CN102516809A - Method for producing nanoparticles by forced ultra-thin film rotary processing - Google Patents

Abstract

A method for producing nanoparticles is characterized in that two processing surfaces capable of approaching each other and separating from each other and rotating relative to each other are held with a small gap of 1 mm or less, that the space between the surfaces is used as a passage for a fluid under processing, and that a forced thin film of the fluid is formed and nanoparticles are precipitated in the forced thin film.

Description

Use the method for manufacture of the particulate of forced ultra-thin film rotary processing

The national applications that the application is is on July 4th, 2008 applying date, get into China's stage number is 200880105423.2, invention and created name is divided an application for the patented claim of " using the method for manufacture of the nanoparticle of forced ultra-thin film rotary processing ".

Technical field

The application invention relates to the nanoparticle method of manufacture of carrying out the processing of object being treated with the processing in the portion between with face through in the processing that can relatively be rotated with respect to the opposing party near isolating at least one side.

Background technology

Non-patent literature 1: Junichiro Koizumi's light favour (etc.) work, " Na ノ マ テ リ ア Le state-of-the-art technology ", the 1st edition, the シ of Co., Ltd. one エ system シ one publishes, April calendar year 2001

Non-Patent Document 2: Nanotechnology Handbook Editorial Board, "Nano black Bruno Te Hana nn ro ji a cloth sleeve boots choreography ru ku-I", 1st Edition, Io a Charm Corporation Ltd., May 2003

Patent documentation 1: the spy opens flat 7-144102 communique

Patent documentation 2: the spy opens the 2002-97281 communique

Patent documentation 3: the spy opens the 2007-8924 communique

Patent documentation 4: the spy opens the 2004-49957 communique

Volume average particle size in the size-grade distribution less than the particulate of 1 μ m (below; Be called nanoparticle among the application), the nanoparticle below the 100nm particularly; Because the ionic surface-area sharply increases, occurs new characteristic with respect to the ratio of volume, so independent nanoparticle or its aggregate, organic and inorganic complex body etc., in nano material, express very big expectation (non-patent literature 1) as the material of 21 century.That is, owing to, just can make this material present new function only through inciting somebody to action corpuscleization in the past; Therefore become important theme at whole industry circle nanoparticle; In addition, aspect the promotion nanotechnology, with the relation indivisible certainly (non-patent literature 2) of particulate, particularly nanoparticle.

Therefore, hope to make the novel manufacturing method of particulate.And then, in order in industry, to apply flexibly, establish stably and the method for manufacture of producing in a large number is a most important problem in the nanotechnology.

As the method for in liquid, making particulate, just like shown in the patent documentation 1 on one side stirring and dissolving the solution of specific solute, on one side utilize the method that for the poor solubility of solute particulate is separated out owing to solvent that temperature head produced.In the method, utilization is: solvent is at a certain temperature separated out in solvent for the solubleness of the solute solute that solubleness reduces, surpasses the amount of saturation solubility through the temperature that reduces solvent.But, because this method is used the general still with phaudler wing, be difficult to make the particle of nano-scale in fact, in addition so that crystallization is separated out under the situation as purpose, it is even that its crystal type is difficult to become.Therefore; Like patent documentation 2; Organism is dissolved in organic solvent, and the method for the solvent that this organic solution injection solubleness is also lower than above-mentioned organic solvent is promptly through mixing for the solubleness of solute high good solvent and the low poor solvent of solubleness; Reduce the apparent solubility of good solvent, make above the solute of saturation solubility separate out and the method that obtains particulate for generally becoming common.But above-mentioned 2 kinds of methods all are the methods that reaction vessel and the reaction kettle with so-called batch of formula separated out material, stably make the particulate of nano-scale or crystal type etc. is very difficult uniformly.Its reason is caused by following: general use stirring operation batch in the situation of evolution reaction under, in its batch, must produce uneven homogenize because of thermograde or concentration gradient, the reacting field that causes thus.Therefore, the temperature treatment in batch, concentration management be difficulty very, must be difficult to react uniformly.Therefore, must prolong the necessity in reaction times etc., it is very difficult that whole reaction conditionss is managed.

In addition, of patent documentation 3, have that to use microresponse device, small stream formula reactor drum be that micro mixer or microreactor utilize poor solubility and obtain the method for particulate.But; Under the situation of using general microreactor; Though the advantage of micro element and system has, if in fact the microfluidic circuit diameter becomes narrow more, 4 powers of its pressure-losses and stream are inversely proportional to; Promptly in fact be difficult to obtain to send into the fluidic pump and the big liquor charging pressure of needs; In addition under situation with the reaction of separating out, the microfluidic circuit that product latch up phenomenon or bubble of taking place because of reaction in stream cause close so that basically in expectation this reaction aspect the velocity of diffusion of molecule, it is effective suitable therefore for whole reactions, can not to say so between microvoid; Exist in tentative reaction in the TE mode in the reality, select the good necessity of head and the tail etc., its problem is also many.Even and then for amplifying (scale up), increase the quantity of microreactor itself method, promptly solve through range upon range of (numbering up), think that tens of layers is boundary but in fact can layer close number; The range upon range of costly goods of goods that only are used for; In addition, device increases, and the absolute number of its fault cause also increases; In fact under the situation of the problem of take place stopping up etc., find its position of fault etc., problem location very difficulty that possibly become.

Summary of the invention

The invention solves in the past the technical task or the problem points that are referred to as " little chemical process technology (マ イ Network ロ chemistry プ ロ セ ス technology) "; Little chemical process technology based on novel concept; More specifically, purpose provides the deposition method of mixed uniformly nano particle of principle stirring that carry out, that used multiple fluid in small stream moment of a kind of the application's of use the patent documentation that the applicant applied for 4 shown devices.This device utilizes the principle of mechanical seal, below the realization: form the pressure film that is processed liquid between can be near the processing use face of relative displacement discretely, be processed liquid to supplying with between the processing use face that is rotated, supply with through this fluidic press with the processing use face that is being rotated between the pressure equilibrium of applied pressure make the distance between processing use face be slight gap.Compare with the method in the above-mentioned principle; Method is in the past handled with the methods such as distance between the face for mechanically regulating it; Can not absorb heat that rotation produces and because of the distortion of its generation; And center runout etc., make distance between small processing use face, at least this distance be come down to below the 10 μ m impossible.Promptly; Utilize the principle of above-mentioned patent documentation 4 said devices; Make the realization of separating out of nanoparticle of the chemistry that in small stream, utilizes moment and physicochemical reaction etc. become possibility; The application contrivers etc. are through further investigation, from needless to say, surprisingly can carry out moment in the small stream of 0.1～10 μ m to mix and separate out below the 1mm.And produce the ideal that is called " little chemical process technology " in essence through the present invention and separate out condition.The application's purpose is: use in can be near the film fluid that subtend processing that set, that at least one side relatively is rotated with respect to the opposing party produces between with face each other discretely to make particulate separate out such novel method, make nanoparticle.

In order to solve above-mentioned problem; The invention that the application's the 1st invention is put down in writing; The method of manufacture of nanoparticle is provided, it is characterized in that, through between 2 processing can keeping slight gap below the 1mm near 2 processing that relatively be rotated discretely between with face, will keep with this slight gap are with face as the stream that is processed liquid; Formation is processed the pressure film of liquid, in this pressure film, carries out separating out of nanoparticle.

In addition; The application the 2nd invents the invention of being put down in writing, and the method for manufacture of nanoparticle is provided, and it is characterized in that; Can near 2 processing of isolating relative displacement with face between the multiple liquid that is processed of supply; Through the supply that contains this liquid press and between rotation treatment is with face applied pressure to the power of direction of closing and equilibrium of forces to detaching direction, keep processing with the distance between face with slight gap, 2 processing will keeping with this slight gap with between face as the above-mentioned stream that is processed liquid; Form the pressure film that is processed liquid thus; In this pressure film, carry out separating out of nanoparticle, any of above-mentioned multiple liquid all do not contain the particle greater than the nanoparticle that obtains.

In addition; The invention that the application's the 3rd invention is put down in writing; Provide the application to invent the method for manufacture of 1 to 2 nanoparticle put down in writing; It is characterized in that, comprise the liquid that is processed of multiple liquid, carry out separating out of nanoparticle with the state that has been stirred, has mixed in the above-mentioned pressure film between face in 2 above-mentioned processing.

In addition, the invention that the application's the 4th invention is put down in writing provides the application to invent the method for manufacture of each nanoparticle of putting down in writing in 1 to 3, it is characterized in that the volume average particle size in the size-grade distribution of the nanoparticle that obtains is 1nm～200nm.

In addition; The invention that the application's the 5th invention is put down in writing; Provide the application to invent the method for manufacture of each nanoparticle of putting down in writing in 1 to 4, it is characterized in that, contain the liquid that is processed of nanoparticle after separating out; After 2 above-mentioned processing further are stirred in the above-mentioned pressure film between face, from handling with being discharged between face.

The invention that the application's the 6th invention is put down in writing; Provide the application to invent the method for manufacture of 2 nanoparticles put down in writing; It is characterized in that; Use following forced ultra-thin film rotating treatment unit: possess and give the fluid of pressure and press imparting mechanism, the 1st to handle with portion and can handle with portion with respect to the 1st and relatively handle with at least 2 processing of portion with portion, rotary drive mechanism that said the 1st processing relatively is rotated with portion with portion and the 2nd processing near the isolating the 2nd to being processed liquid; Described each handle with in the portion each other the position of subtend be provided with the 1st and handle to handle and use face with at least 2 processing of face, a part of using described respectively processing to give the stream that being processed of said pressure is that liquid flows through, quilt is sealed with the face formation with face and the 2nd; Described two handle with face between with being processed the liquid uniform mixing, separating out more than 2 kinds; Said the 1st processing is handled with at least the 2 processing in the portion with portion and the 2nd possesses load face with portion; And at least a portion of this load face is handled by the described the 2nd and is constituted with face; This load face; Receiving described fluid pressure imparting mechanism gives the pressure that is processed liquid and produces the power that the 2nd processing is moved with the isolating direction of face from the 1st processing with face 2; Through can near separate and relatively be rotated the 1st handle that feeding is described between handling with face with face and the 2nd is processed liquid more than 2 kinds; This is processed liquid and passes through two while the film fluid that forms the regulation thickness and handle with between face, carries out the separating out of nanoparticle with the state that has been stirred, has mixed in said 2 processing in the said pressure film between face.

In addition, the invention that the application's the 7th invention is put down in writing provides the application to invent the method for manufacture of each nanoparticle of putting down in writing in 1 to 6, it is characterized in that any of above-mentioned multiple liquid all do not contain than do not obtain the big particle of nanoparticle.

The application invention through the liquid that is processed more than two kinds is mixed and reacts etc., is separated out small nanoparticle thus in above-mentioned pressure film.These are multiple is processed liquid; Can drop into other the liquid that is processed being processed in the liquid more than a kind in the path between face in above-mentioned 2 processing that relatively are rotated; Dropped into both before perhaps just between handling, and then mix in advance before between handling with face reaching, but can receive the effect of mixing in the pressure film between face in these 2 processing that relatively are rotated with face; Realize preferred admixture thus, realize the good effect of separating out.Particularly; Above-mentioned multiple any of liquid of being processed; All do not contain the particle also bigger,, carry out separating out of small nanoparticle in above-mentioned pressure film through the liquid that is processed more than two kinds is mixed and reacts etc. than the nanoparticle that obtains; Through correctly controlling its condition, can obtain nanoparticle as the particle diameter of purpose.And, separate out owing to carry out this in the path between face in 2 processing that relatively are rotated, do not produce inaccessible such state of affairs generation of the microfluidic circuit that product causes, production serially.In addition, according to condition, also sometimes between 2 processing that relatively are rotated are with face, apply the effect of stirring, dispersion, micronize etc. for the nanoparticle of separating out.

Description of drawings

Fig. 1 (A) is the simple longitudinal diagram of the notion of the expression device that is used to implement the application's invention; (B) be the simple longitudinal diagram of notion of other embodiments of expression said apparatus; (C) being the simple longitudinal diagram of notion of further other embodiment of expression said apparatus, (D) is the simple longitudinal diagram of notion of another other embodiments of expression said apparatus.

Fig. 2 (A)～(D) is respectively the simple longitudinal diagram of notion of further other embodiment of presentation graphs 1 shown device.

Fig. 3 (A) is the simple upward view of the major portion of Fig. 2 (C) shown device; (B) be the simple upward view of major portion of other embodiments of said apparatus; (C) be the simple upward view of the major portion of further other embodiment; (D) be the simple upward view of notion of another other embodiments of expression said apparatus; (E) being the simple upward view of notion of another other embodiments of expression said apparatus, (F) is the simple upward view of notion of another other embodiments of expression said apparatus.

Fig. 4 (A)～(D) is respectively the simple longitudinal diagram of notion of further other embodiment of presentation graphs 1 shown device.

Fig. 5 (A)～(D) is respectively the simple longitudinal diagram of notion of further other embodiment of presentation graphs 1 shown device.

Fig. 6 (A)～(D) is respectively the simple longitudinal diagram of notion of further other embodiment of presentation graphs 1 shown device.

Fig. 7 (A)～(D) is respectively the simple longitudinal diagram of notion of further other embodiment of presentation graphs 1 shown device.

Fig. 8 (A)～(D) is respectively further other the simple longitudinal diagram of notion of embodiment of presentation graphs 1 shown device.

Fig. 9 (A)～(C) is respectively further other the simple longitudinal diagram of notion of embodiment of presentation graphs 1 shown device.

Figure 10 (A)～(D) is respectively further other the simple longitudinal diagram of notion of embodiment of presentation graphs 1 shown device.

Figure 11 (A) reaches the simple longitudinal diagram of the notion of another other embodiments of (B) representing above-mentioned device shown in Figure 1 respectively, (C) is the simple upward view of the major portion of Fig. 1 (A) shown device.

Figure 12 (A) is the simple longitudinal diagram about major portion load face, that represent other embodiments of Fig. 1 (A) shown device, (B) is the simple longitudinal diagram of major portion of another other embodiments of this device.

Figure 13 is the simple longitudinal diagram that touches major portions surface pressure imparting mechanism 4, other embodiments about the connection of Figure 12 (A) shown device.

Figure 14 about on Figure 12 (A) shown device, be provided with the simple longitudinal diagram of temperature regulation with major portions big envelope, other embodiments.

Figure 15 is about the pressure of contact surface imparting mechanism 4 of Figure 12 (A) shown device, main simple longitudinal diagram of other embodiments.

Figure 16 (A) is the simple drawing in side sectional elevation of major portion of another other embodiments of Figure 12 (A) shown device; (B) (C) (E)～(G) is the simple drawing in side sectional elevation of major portion of another other embodiments of this device, (D) is the simple longitudinal diagram of partial major portion of another other embodiments of this device.

Figure 17 is main a simple longitudinal diagram of another other embodiments of Figure 12 (A) shown device.

Figure 18 (A) is the simple longitudinal diagram of notion of another other embodiments of the expression device that is used for the application's working of an invention, (B) is the partial major portion explanatory view of this device.

Figure 19 (A) is the vertical view that the 1st of said apparatus shown in Figure 12 is handled with portion, (B) is the longitudinal diagram of its major portion.

Figure 20 (A) is the longitudinal diagram that the 1st and the 2nd of device shown in Figure 12 is handled with the major portion of portion, (B) is to separate main the longitudinal diagram that the above-mentioned the 1st and the 2nd of slight gap is handled with portion.

Figure 21 (A) is the vertical view of above-mentioned the 1st processing with other embodiments of portion, (B) is the simple longitudinal diagram of its major portion.

Figure 22 (A) is the vertical view of above-mentioned the 1st processing with another other embodiments of portion, (B) is the simple longitudinal diagram of its major portion.

Figure 23 (A) is the vertical view of above-mentioned the 1st processing with another other embodiments of portion, (B) is the vertical view of above-mentioned the 1st processing with another other embodiments again of portion.

Figure 24 (A) (B) (C) is respectively explanatory view separation method, the above-mentioned embodiment in addition of expression about the object being treated after handling.

Figure 25 is the sketch chart in longitudinal section of the summary of explanation the application contrive equipment.

Figure 26 (A) is the simple vertical view that the 1st of device shown in Figure 25 is handled with face, (B) is the expanded view that the 1st of device shown in Figure 25 is handled with the major portion of face.

Figure 27 (A) is the sectional view of the 2nd introduction channel, (B) is to be used to explain the expanded view of the processing of the 2nd introduction channel with the major portion of face.

It (B) is respectively to be arranged at the major portion expansion sectional view of handling with the scarp of portion in order to explain that Figure 28 (A) reaches.

Figure 29 is used to explain be arranged at the figure that handles with the load face of portion, is the upward view of the 2nd processing with portion (A), (B) is the expansion sectional view of major portion.

Figure 30 is the electron micrograph of pigment nanoparticle.

Figure 31 is the electron micrograph of pigment nanoparticle.

Figure 32 is the electron micrograph of pigment nanoparticle.

Figure 33 is the TEM photo of silver particles.

Figure 34 is the TEM photo of platinum particulate.

Figure 35 is the TEM photo of platinum particulate.

Figure 36 is the TEM photo of platinum-palldium alloy particulate.

Figure 37 is the TEM photo of platinum-palldium alloy particulate.

Figure 38 is the TEM photo of nickel particle.

Figure 39 is the TEM photo of particulate.

Figure 40 is the microphotograph of the emulsion that relates to of embodiment L1.

Figure 41 is the microphotograph of the emulsion that relates to of embodiment L2.

Embodiment

As used in the present invention, can be near the method that each other evenly mixes in the subtend film fluid that set, that at least one processing that can be rotated with respect to the opposing party forms between with face discretely, for example can use with applicant of the present invention, the spy opens the device put down in writing in the 2004-49957 communique device with principle.

Below, the fluid treating device of the enforcement that is suitable for this method is described.

Shown in Fig. 1 (A), this device has 2 processing of the 1st and the 2nd of subtend with portion 10,20, and at least one side's processing is rotated with portion.Two handle subtend face with portion 10,20 respectively as handling with face 1,2, between two processing are with face, are processed the processing of liquid.The 1st processing has the 1st processing with portion 10 and has the 2nd processing with face 2 with face 1, the 2 processing with portion 20.

Two processing are connected with the stream that is processed liquid with face 1,2, constitute the part of the stream that is processed liquid.

More detailed, this device constitutes at least 2 streams that are processed liquid, makes each passage confluent simultaneously.

That is, the stream that this device and the 1st is processed liquid connects, form the 1st be processed the stream of liquid a part, form simultaneously and be different from the 1st and be processed the part that the 2nd of liquid is processed the stream of liquid.And this device makes two passage confluents, is handling with face 1, between 2, mixes two liquids and reacts.In the embodiment shown in Fig. 1 (A), above-mentioned each stream is airtight, forms liquid close (being processed the situation that liquid is a liquid) airtight (being processed the situation that liquid is a gas).

If explanation particularly; Shown in Fig. 1 (A); This device has: the above-mentioned the 1st handles with portion 10, the above-mentioned the 2nd and handles with portion 20, keeps 1st carriage 11 of the 1st processing with portion 10, keeps the 2nd processing to give structure p1, the 2nd fluid supply unit p2 and housing 3 with the 2nd carriage 21, pressure of contact surface imparting mechanism 4, rotary driving part, the 1st d1 of importing portion, the 2nd d2 of importing portion, the hydrodynamicpressure of portion 20.

What explain is that rotary driving part omits diagram.

The 1st processing is handled with portion 10 and the 2nd can be with respect to the opposing party be near separating at least arbitrarily with the arbitrary at least of portion 20, and two handle with face 1,2 and can approachingly separate.

In this embodiment, the 2nd handles with portion 20 and can handle with portion 10 near separating with respect to the 1st.But, also can be in contrast, the 1st handles with portion 10 and handles with portion 20 near separating with respect to the 2nd, also can two handles 10, the 20 mutual approaching separation with portion.

The 2nd handles with portion 20 and is configured in the 1st top of handling with portion 10, the 2nd handle face, be lower surface towards the below with portion 20, for the 2nd above-mentioned processing with face 2, the 1 processing with portion 10 towards the face of top, promptly above, for the 1st above-mentioned processing with face 1.

Shown in Fig. 1 (A), in this embodiment, the 1st processing is handled with portion 10 and the 2nd and is respectively ring bodies with portion 20, i.e. annulus.Below, as required, claim that the 1st processing use portion 10 is the 1st annulus 10, claim that the 2nd processing use portion 20 is the 2nd annulus 20.

In this embodiment, two annulus the 10, the 20th, a metal end face are handled with face 2 with face 1 and the 2nd as the 1st processing with this minute surface by the member of mirror ultrafinish.That is, handle with face 1 as the 1st the upper surface of the 1st annulus 10, and by mirror ultrafinish, handle with face 2, by mirror ultrafinish as the 2nd the lower surface of the 2nd annulus 20.

At least one side's carriage can relatively be rotated through the carriage of rotary driving part with respect to the opposing party.The turning axle of the 50 expression rotary driving parts of Fig. 1 (A).In rotary driving part, can adopt phonomoter.Through rotary driving part, the processing of a side annulus relatively is rotated with face with the processing of face with respect to the opposing party's annulus.

In this embodiment, the 1st carriage 11 receives the motivating force from rotary driving part through turning axle 50, be rotated with respect to the 2nd carriage 21, like this and the 1st annulus 10 that is integrally formed of the 1st carriage 11 with respect to 20 rotations of the 2nd annulus.In the inboard of the 1st annulus 10, turning axle 50 is arranged on the 1st carriage 11 as follows, that is, when overlooking, the centres of the 1st annulus 10 of its center and circle.

The rotation of the 1st annulus 10 is the center with the axle center of the 1st annulus 10.Though not shown, still, the axle center refers to the medullary ray of the 1st annulus 10, is imaginary line.

As stated, in this embodiment, the 1st carriage 11 is handled with face 1 towards the top the 1st of the 1st annulus 10, and keep the 2nd processing that the 1st annulus 10, the 2 carriages 21 make the 2nd annulus 20 with face 2 towards the below, and keep the 2nd annulus 20.

Be specially, the 1st and the 2nd carriage 11,21 has the annulus resettlement section of concavity respectively.In this embodiment, the 1st annulus 10 is embedded in the annulus resettlement section of the 1st carriage 11, and the 1st annulus 10 is fixed in the annulus resettlement section, thereby can not haunt from the annulus resettlement section of the 1st carriage 11.

That is, above-mentioned the 1st processing is exposed from the 1st carriage 11 with face 1, towards the 2nd carriage 21 sides.

The material of the 1st annulus 10 also can adopt other metals that pottery, sintering metal, wear resisting steel, enforcement overcuring handle, or apply, coats, is electroplate with the material of mechanically resistant material except metal.Particularly, because rotation, the most handy light-weight raw material forms the 1st handling part 10.About the material of the 2nd annulus 20, also can adopt the material identical with the 1st annulus 10.

On the other hand, the annulus resettlement section 41 that had of the 2nd carriage 21 can accommodate the 2nd annulus 20 with haunting processing with face 2.

The annulus resettlement section 41 that the 2nd carriage 21 is had be accommodate the 2nd annulus 20, mainly be and handle recess with face 2 side opposition side positions, rounded when overlooking, promptly form the cyclic groove.

The size of annulus resettlement section 41 is bigger than the 2nd annulus 20, and between the 2nd annulus 20 enough intervals is arranged, and accommodates the 2nd annulus 20.

Through this at interval, in this annulus resettlement section 41, the 2nd annulus 20 can be at the direction of principal axis of cyclic annulus resettlement section 41 and in the direction displacement that intersects with this direction of principal axis.In other words, through this at interval, the medullary ray that the 2nd annulus 20 can make the 2nd annulus 20 with the mode that changes with the axial parallel relation of above-mentioned annulus resettlement section 41 is with respect to 41 displacements of annulus resettlement section.

Below, the position that is centered on by the 2nd annulus 20 of the 2nd carriage 21 is called middle body 22.

For above-mentioned explanation, in other words, the 2nd annulus 20 is housed in the annulus resettlement section 41 as follows; Promptly; Can be the above-mentioned direction displacement of haunting in the thrust direction of annulus resettlement section 41, in addition, can be with respect to the eccentric direction displacement in the center of annulus resettlement section 41.And the 2nd annulus 20 is accommodated as follows, that is, with respect to annulus resettlement section 41, in each position of the circumferential direction of the 2nd annulus 20, can be with the different respectively mode displacement of amplitude of haunting from annulus resettlement section 41, that is, and can the center runout.

Though the 2nd annulus 20 has the degree of freedom of above-mentioned 3 displacements; Promptly; The degree of freedom of the direction of principal axis of 2nd annulus 20 relative, eccentric direction, core runout direction with annulus resettlement section 41, but the 2nd annulus 20 is not to remain on the 2nd carriage 21 with the mode of the 1st annulus 10 rotations.Though not shown, relevant this point as long as on annulus resettlement section 41 and the 2nd annulus 20, with respect to annulus resettlement section 41 suitable tuck is set respectively, thereby is limited in the rotation of its circumferential direction.But this tuck must not destroy the degree of freedom of above-mentioned 3 displacements.

Above-mentioned pressure of contact surface imparting mechanism 4 applies power to handling with portion along the 1st processing is handled with face 2 approaching directions with face 1 and the 2nd.In this embodiment, pressure of contact surface imparting mechanism 4 is arranged on the 2nd carriage 21, and the 2nd annulus 20 is suppressed to the 1st annulus 10.

Pressure of contact surface imparting mechanism 4 suppresses each position of the circumferential direction of the 2nd annulus 20, i.e. the 2nd processing with each position of face 2 equably to the 1st annulus 10.The concrete structure of pressure of contact surface imparting mechanism 4 is described in detail in the back again.

Shown in Fig. 1 (A), above-mentioned housing 3 is configured in the outside of two annulus, 10,20 peripherys, accommodates product, and this product is being handled the outside that generates and be discharged to two annulus 10,20 with face 1, between 2.Shown in Fig. 1 (A), housing 3 is the close containers of liquid of accommodating the 1st carriage 11 and the 2nd carriage 21.The 2nd carriage 21 can be used as the part of this housing and forms with housing 3.

As stated, needless to say form the situation of the part of housing 3, even under situation about forming with housing 3 splits ground, the 2nd carriage 21 is not movable too, thereby can not influence the interval of 10,20 of two annulus, that is, two handle with face 1, interval between 2.In other words, the 2nd carriage 21 can not handled with face 1, interval between 2 two and exert an influence.

On housing 3, the outside of housing 3 is provided with the relief outlet 32 that is used to discharge product.

The 1st d1 of importing portion supplies with the 1st to two processing with face 1, between 2 and is processed liquid.

Above-mentioned hydrodynamicpressure is given structure p1 and is connected with the 1st d1 of importing portion directly or indirectly, is processed liquid to the 1st and applies hydrodynamicpressure.Give among the structure p1 at hydrodynamicpressure, can adopt compressor, other pumps.

In this embodiment, the 1st d1 of importing portion is arranged on the fluid channel of above-mentioned middle body 22 inside of the 2nd carriage 21, and the one of which end is at the central position opening for the 2nd annulus 20 of circle of overlooking of the 2nd carriage 21.In addition, the other end of the 1st d1 of importing portion in the outside of the 2nd carriage 21, be that the outside of housing 3 is given structure p1 with above-mentioned hydrodynamicpressure and is connected.

The 2nd d2 of importing portion is to handling the 2nd liquid that is processed the liquid reaction with face with 1,2 supply and the 1st.In this embodiment, the 2nd importing portion is the fluid channel that is arranged on the 2nd annulus 20 inside, and the one of which end is handled with face 2 openings the 2nd, and its other end is connected with the 2nd fluid supply unit p2.

In the 2nd fluid supply unit p2, can adopt other pumps such as compressor.

Give the 1st of structure p1 pressurization through hydrodynamicpressure and be processed liquid and be imported into the space of the inboard of two annulus 10,20, handle with face 1 and the 2nd processing with between the face 2 through the 1st, pass from the outside of two annulus 10,20 from the 1st d1 of importing portion.

At this moment, receive the 1st be processed the transfer pressure of liquid the 2nd annulus 20 overcome suppressing of pressure of contact surface imparting mechanism 4, away from the 1st annulus 10, make two to handle with separating small interval between face.About because of two handle with face 1,2 near separating two processing that form with face 1, interval between 2, be described in detail again at the back.

Handle with 1,2 in face two, from the 2nd d2 of importing portion supply with the 2nd be processed liquid and with the 1st be processed the liquid interflow, utilize the rotation promotion of handling with face to react.Then, the reaction product that reaction generated of two liquids is from two handling with face 1, being discharged to the outside of two annulus 10,20 between 2.The reaction product of discharging in two annulus, 10,20 outsides finally is discharged to the outside of housing 3 through the relief outlet 32 of housing 3.

Above-mentioned mixing that is processed liquid and reaction through with the 2nd handle the 1st relative rotation that is produced by driving part 5 handled with portion 10 with portion 20, carry out with face 2 with face 1 and the 2nd processing in the 1st processing.

Handle with face 1, between 2 the 1st and the 2nd, the downstream side of the peristome m2 of the 2nd d2 of importing portion forms reaction chamber, and this reaction chamber makes the above-mentioned the 1st to be processed liquid and the 2nd and to be processed liquid and to react.Particularly; Handle with face 1, between 2 two; On the inward-outward direction r1 of the 2nd annulus 20 diameters of in Figure 11 (C) of bottom surface of expression the 2nd annulus 20, representing with oblique line, the peristome m2 of the 2nd importing portion, promptly the exterior lateral area H of the 2nd peristome m2 has as above-mentioned treatment chamber, is the function of reaction chamber.Therefore, this reaction chamber is handled with face 1 two, is positioned at the 1st d1 of importing portion and the two peristome m1 of the 2nd d2 of importing portion, the downstream side of m2 between 2.

Be directed into two processing from the 2nd peristome m2 and be processed liquid with face 1, the 2nd between 2; In the regional H of above-mentioned formation reaction chamber; Be directed into two from the 1st peristome m1 through the inboard spatial of annulus and handle and be processed liquid with face 1, the 1st between 2 and mix, two are processed liquid reacts.Liquid is given structure p1 through hydrodynamicpressure and is received transfer pressure, and in two handle with face 1, slight gap between 2 towards the outer side shifting of annulus, still; Because 10 rotations of the 1st annulus, so, in above-mentioned conversion zone H; Mixed liquid is not on the inward-outward direction of circle diameter, to move point-blank laterally from the inboard; But overlook under the state of handling with face, be the center with the turning axle of annulus, helically is mobile laterally from the inboard of annulus.Like this, carrying out the regional H of hybrid reaction, moving laterally from the inboard of annulus, thereby can guarantee in two handle with face 1, slight gap between 2, to have the needed interval of abundant reaction, and can promote its uniform reaction through helically.

In addition, the product that reaction produces is in the above-mentioned the small the 1st and the 2nd reaction product handled with 1,2 formation of face homogeneous, particularly under crystallization or situation about separating out, forms particulate.

At least; Give at above-mentioned hydrodynamicpressure on the isostatic basis of the cf-that rotation produced of reactive force and annulus of the transfer pressure of structure p1 load, above-mentioned pressure of contact surface imparting mechanism 4; Can make two handle with face 1, between 2 spaced equalized and become preferred slight gap; And; Receive hydrodynamicpressure give structure p1 load transfer pressure and annulus the cf-that rotation produced be processed liquid, helically moves in face 1, slight gap between 2 in above-mentioned processing, promotes to react.

Above-mentioned reaction is given the rotation of transfer pressure that structure p1 loads and annulus through hydrodynamicpressure and is carried out by the strong hand.That is, be reflected at the processing that can set near subtend discretely and at least one side is rotated with respect to the opposing party with 1,2 in face, and meanwhile by the strong hand uniform mixing take place

So, particularly, through hydrodynamicpressure give adjustment and the annulus of the structure transfer pressure that p1 is loaded speed of rotation, be the method that this ratio of adjustment of the rotating speed of annulus is easier to control, the crystallization of the product of may command reaction or separate out.

Like this; This treatment unit is through the adjustment of transfer pressure and cf-; The processing of the size of carrying out product is exerted an influence is with face 1, the control at interval between 2, and, very excellent aspect the control of the miles of relative movement in the above-mentioned conversion zone H of the even generation that influences product.

In addition, the material that the product of above-mentioned reaction treatment is not limited to separate out also comprises liquid.

What explain is that turning axle 50 is not limited to arranged perpendicular, also can be configured in horizontal direction, also tiltable configuration.In the processing, be illustrated as two and handle the situation of reacting, can get rid of the influence of gravity in fact with in face 1, the slight gap between 2.

The 1st represented among Fig. 1 (A) d1 of importing portion representes following mechanism, and is promptly consistent with the axle center of the 2nd annulus 20 in the 2nd carriage 21, and court is the mechanism of vertical extension up and down.But; The 1st d1 of importing portion is not limited in the mechanism consistent with the axle center of the 2nd annulus 20; So long as can to the space that two annulus 10,20 are surrounded supply with the 1st be processed liquid mechanism get final product; Also can be arranged on other positions of the middle body 22 of the 2nd carriage 21, in addition, the device of extension that also can the vertical inclination of right and wrong.

The preferred embodiment of Figure 12 (A) expression said apparatus.As shown in the figure, the 2nd handles and to have the above-mentioned the 2nd with portion 20 and handle with face 2, and has load face 23, this load face 23 be positioned at the 2nd handle with the inboard of face 2 and with the 2nd processing with face 2 adjacency.Below, this load face 23 is called again and separates with adjustment face 23.As shown in the figure, this separation uses adjustment face 23 to be the scarp.

As previously mentioned, in the bottom of the 2nd carriage 21, be the bottom, form annulus resettlement section 41, contain the 2nd in this annulus resettlement section 41 and handle with portion 20.In addition, though do not illustrate,, the 2nd processing is not accommodated rotatably with respect to the 2nd carriage 21 with portion 20 through the rotation stopping device.Above-mentioned the 2nd processing is exposed from the 2nd carriage 21 with face 2.

In this embodiment, handle use face 1, between 2, the 1st handle use portion 10 and the 2nd and handle the inflow portion of the inboard of portion 20 that use as object being treated, the 1st handles use portion 10 and the 2nd handles the outflow portion of the outside of portion 20 as object being treated that use.

Above-mentioned pressure of contact surface imparting mechanism 4 pushings the 2nd are handled with face 2; It is handled with respect to the 1st be in the approaching state of crimping with face 1; Make two to handle through this pressure of contact surface and hydrodynamicpressure etc., form the film fluid of stipulating thickness with face 1, isolating equilibrium of forces between 2.In other words, through above-mentioned equilibrium of forces, two handle with face 1, interval between 2 and remain predetermined slight gap.

Particularly, in this embodiment, pressure of contact surface imparting mechanism 4 is by constituting with the lower section: above-mentioned annulus resettlement section 41; Clockwork spring resettlement section 42, the inside that this clockwork spring resettlement section 42 is arranged on annulus resettlement section 41 is the innermost of annulus resettlement section 41; Spring 43; And, air importing portion 44.

But pressure of contact surface imparting mechanism 4 also can only have any at least in above-mentioned annulus resettlement section 41, above-mentioned clockwork spring resettlement section 42, spring 43 and the air importing portion 44.

Handle with portion's 20 running fit annulus resettlement section 41 and the 2nd, thereby the dark or shallow ground displacement with the position of portion 20 is handled in the 2nd in the annulus resettlement section 41, gets final product upper and lower displacement.

One end of above-mentioned spring 43 and the inside butt of clockwork spring resettlement section 42, the front portion that handle with portion 20 the 2nd in the other end of spring 43 and the annulus resettlement section 41 is the top butt.In Fig. 1,, but preferably push the various piece of the 2nd processing with portion 20 through a plurality of springs 43 though spring 43 only shows 1.That is,, can give the 2nd and handle impartial more thrust pressure with portion 20 through increasing the number of spring 43.So preferred the 2nd carriage 21 is for installing several compound to dozens of spring 43.

In this embodiment, also can in annulus resettlement section 41, import air through above-mentioned air importing portion 44.Through the importing of such air, with annulus resettlement section 41 and the 2nd handle with between the portion 20 as the pressurized compartment, spring 43 is put on the 2nd processing with in the portion 20 with air pressure as thrust pressure.Therefore,, can adjust in the running the 2nd and handle with face 2 from the air pressure that air importing portion 44 imports through adjustment with respect to the pressure of contact surface of the 1st processing with face 1.And, replace utilizing the air importing portion 44 of air pressure, the mechanism that produces thrust pressure through other hydrodynamicpressure such as oil pressure also capable of using.

Pressure of contact surface imparting mechanism 4 is gone back double as displacement adjustment mechanism and buffer gear except supplying with and regulating the part that above-mentioned thrust pressure is a pressure of contact surface.

In detail, pressure of contact surface imparting mechanism 4 is followed the stretching, extension that starting when and turn round central axis direction or is worn and torn caused axial displacement through the adjustment that air is pressed as the displacement adjustment mechanism, can keep the thrust pressure at initial stage.In addition, as stated, pressure of contact surface imparting mechanism 4 also has the function as the buffer gear of little vibration and positioning of rotating because employing keeps the relocation mechanism of the 2nd processing with portion 20 movablely.

Then, the user mode about the treatment unit that adopts said structure describes according to Fig. 1 (A).

At first, the 1st is processed liquid receives the transfer pressure of giving structure p1 from hydrodynamicpressure, imports the internal space of closed shell through the 1st d1 of importing portion.On the other hand, through the rotation by the turning axle 50 that rotary driving part produced, the 1st handles 10 rotations with portion.Thus, the 1st processing is handled with face 2 rotation relatively under the state that keeps slight gap with face 1 and the 2nd.

The 1st is processed liquid forms the film fluid in two processing of maintenance slight gap with face 1, between 2, be processed liquid from the 2nd of the 2nd d2 of importing portion importing and handle with face 1 two, collaborate with this film fluid between 2, and it is a part of to constitute the film fluidic equally.Through this interflow, the 1st and the 2nd is processed liquid mixes, and two fluids react, and promote homogeneous reaction, form its reaction product.Thus, under with situation about separating out, can be formed uniformly fine particle, even, still can realize uniform reaction under situation about separating out.In addition, the reaction product of separating out is owing to the 1st processing is sheared with 2 in face at itself and the 2nd processing with the rotation of face 1, sometimes by further micro.At this, be adjusted into 1 μ m to 1mm, the particularly slight gap of 1 μ m to 10 μ m through handling the interval of handling with face 2, thereby can realize uniform reaction with face 1 and the 2nd with the 1st, simultaneously, can generate the ultra micron of number nm unit.

Product is handled with face 1, discharge between 2 from two, and the discharge 32 through housing 3 is discharged to outside.Product after the discharge forms vaporific in vacuum or post-decompression environment through known reliever, become fluid after other parts in running into environment and flow down, and the liquid object that can be used as after the degasification is recovered.

In addition, in this embodiment,, also such housing 3 can be set though treatment unit has housing 3.For example, the relief groove that degasification is used can be set, i.e. vacuum tank, and portion's configuration process device within it.In this case, on treatment unit, do not have above-mentioned relief outlet certainly.

As stated, can handle the interval of handling with face 2 with face 1 and the 2nd with the 1st and be adjusted into the slight gap that the μ m unit that can not reach is set at mechanical interval, its structure explanation as follows.

The 1st processing is handled with face 2 and can relatively approachingly be separated with face 1 and the 2nd, and rotation relatively.In this example, the 1st handles with face 1 rotation, and the 2nd processing is slided at direction of principal axis with face 2, handles with face 1 near separating with respect to the 1st.

Therefore, in this example, the 2nd handles with the direction of principal axis position of face 2 and passes through equilibrium of forces, promptly above-mentioned pressure of contact surface with separate equilibrium of forces, be set at the precision of μ m unit, thereby handle with face 1, the setting of slight gap between 2.

Shown in Figure 12 (A),, can enumerate following instance: in pressure of contact surface imparting mechanism 4, press, promptly apply this pressure under the barotropic condition from the air that air importing portion 44 applies as pressure of contact surface; And, the thrust pressure of spring 43.

In addition, in the embodiment shown in Figure 12～15,, omitted describing of the 2nd d2 of importing portion for avoiding the numerous and diverse of drawing.About this point, also can regard the section of the position that the 2nd d2 of importing portion is not set as.In addition, among the figure, U representes the top, and S representes the below.

On the other hand, as separating force, can enumerate following instance: act on the load face that separates side, promptly the 2nd handle with face 2 and separation with the hydrodynamicpressure on the adjustment face 23; The 1st handles the cf-that rotation produced with portion 10; And, air importing portion 44 is applied this negative pressure under the situation of negative pressure.

Moreover, when device is cleaned, put on the negative pressure of above-mentioned air importing portion 44 through increase, can strengthen two separation handled with face 1,2, can easily clean.

And,, the 2nd processing is in respect to the 1st processing with face 2 unchangeably separates the position of predetermined slight gap, thereby realize the setting of μ m unit precision with face 1 through these equilibrium of forces.

Separating force is explained as follows in further detail.

At first, about hydrodynamicpressure, the 2nd processing in the sealing stream receives with portion 20 and comes from the pressure of sending into that is processed liquid that hydrodynamicpressure is given structure p1, i.e. hydrodynamicpressure.At this moment, become the load face that separate side with face 2 with separating with adjustment face 23 with the relative face of face, i.e. the 2nd processing with the processing of the 1st in the stream, fluid pressure action is on this load face, and generation is pressed caused separating force because of fluid.

Secondly, about cf-, if the 1st handle with portion's 10 high speed rotating, then centrifugal action is in fluid, and the part of this cf-becomes separating force, this separating force act on two handle with face 1,2 mutual away from direction on.

In addition, when handling when applying negative pressure with portion 20 to the 2nd from above-mentioned air importing portion 44, this negative pressure works as separating force.

More than, in the explanation of the application's invention, the masterpiece that the 1st and the 2nd processing use face 1,2 is separated from each other is described for separating force, be not that the power of above-mentioned expression is got rid of from separating force.

As stated; In the stream that is processed liquid of sealing, via handling with face 1, being processed liquid between 2, the pressure of contact surface that formation separating force and pressure of contact surface imparting mechanism 4 are given reaches the equilibrated state; Thereby; Handle with face 1 two, realize homogeneous reaction between 2, simultaneously, form the film fluid that is fit to carry out the crystallization of microresponse product or separates out.Like this, this device is got involved the film fluid by the strong hand through handling two with face 1, between 2, and the slight gap that can not realize in the device of machinery that can be in the past maintains two processing with face 1,2, thereby realization generates the particulate as reaction product accurately.

In other words, handle with face 1, the adjustment of film fluidic thickness through above-mentioned separating force and pressure of contact surface between 2 and be adjusted to preset thickness, can realize required homogeneous reaction and carry out the generation processing of small product.So; Under the situation that will form little film fluidic thickness, as long as adjustment pressure of contact surface or separating force get final product thereby pressure of contact surface is increased with respect to separating force; On the contrary; Under the situation that will form big film fluidic thickness, as long as adjustment pressure of contact surface or separating force get final product thereby separating force is increased with respect to pressure of contact surface.

Increasing under the situation of pressure of contact surface, in pressure of contact surface imparting mechanism 4, give air from air importing portion 44 and press, be malleation, perhaps, spring 43 changed to the big spring of thrust pressure or increase its number get final product.

Under the situation that increases separating force; Can increase hydrodynamicpressure and give the pressure of sending into of structure p1; Perhaps increasing the 2nd handles with face 2, the separation area with adjustment face 23; In addition, thereby can also adjust the rotation increase cf-of the 1st processing, perhaps lower pressure from air importing portion 44 with portion 10.Perhaps, can give negative pressure.Spring 43 is as the thrust clockwork spring that produces thrust pressure at prolonging direction, still, also can be as the pulling force clockwork spring that produces power at shrinkage direction, can form the part or all of the structure of pressure of contact surface imparting mechanism 4.

Reducing under the situation of separating force; Can reduce hydrodynamicpressure and give the pressure of sending into of structure p1; Perhaps reducing the 2nd handles with face 2 or the separation area with adjustment face 23; In addition, thereby can also adjust the rotation minimizing cf-of the 1st processing, perhaps increase pressure from air importing portion 44 with portion 10.Perhaps also can give negative pressure.

In addition, the key element that reduces as the increase of pressure of contact surface and separating force except that above-mentioned, also can add the characteristic that viscosity etc. is processed liquid, and the adjustment of such characteristic that is processed liquid also can be used as the adjustment of above-mentioned key element and carries out.

Moreover, among the separating force, act on the load face that separates side and promptly the 2nd handle the opening force that can be regarded as formation mechanical seal with face 2 and separation with the hydrodynamicpressure on the adjustment face 23.

In mechanical seal, the 2nd processing is equivalent to wear ring with portion 20, and the 2nd processing is being applied under the situation of hydrodynamicpressure with portion 20, handles with the 10 isolating masterpiece times spent of portion with portion 20 and the 1st when effect makes the 2nd processing, and this power is opening force.

More detailed, as the 1st above-mentioned embodiment, when in the 2nd handles with portion 20, only be provided with the load face that separates side, i.e. the 2nd processing with face 2 and the situation of separation with adjustment face 23 under, send into whole formation opening forces of pressure.And, when when the 2nd handles rear side with portion 20 and also load face is set, particularly, after under the situation of Figure 12 (B) of stating and Figure 17, sending among the pressure, as the power of separating force effect and difference formation opening force as the power of pressure of contact surface effect.

At this, use Figure 12 (B) that the 2nd processing other embodiments with portion 20 are described.

Shown in Figure 12 (B), handling the position of exposing and in the inner peripheral surface side from the 2nd with the annulus resettlement section 41 of portion 20, being provided with towards the 2nd opposition side handled with face 2 is the approaching with adjustment face 24 of upper side.

That is, in this embodiment, pressure of contact surface imparting mechanism 4 is by annulus resettlement section 41, air importing portion 44 and above-mentioned near constituting with adjustment face 24.But pressure of contact surface imparting mechanism 4 also can only possess above-mentioned annulus resettlement section 41, above-mentioned clockwork spring resettlement section 42, spring 43, air importing portion 44 and above-mentioned approaching with any at least in the adjustment face 24.

Should be applied to the predetermined pressure that is processed on the liquid near receiving with adjustment face 24; Generation makes the 2nd to handle the power that moves with face 1 approaching direction from the 1st processing with face 2; As an approaching part, the effect of taking on the supply side of pressure of contact surface with pressure of contact surface imparting mechanism 4.On the other hand; The 2nd handle with face 2 with above-mentioned separate to receive with adjustment face 23 be applied to the pressure of being scheduled to that is processed on the liquid; Generation makes the 2nd to handle with face 2 from the 1st processing with the power that face 1 isolating direction moves, and takes on the effect of supply side of the part of separating force.

Receive the above-mentioned load face that is processed the transfer pressure of liquid near being with adjustment face 23 with face 2 and separation with the 24, the 2nd processing of adjustment face, according to its direction, the different effect that realizes producing above-mentioned pressure of contact surface and produce separating force.

Shadow area A1 near with adjustment face 24 is called equilibrium ratio K with the area that adds up to area A 2 than A1/A2; Adjustment to above-mentioned opening force is extremely important; Wherein, Near with the shadow area A1 of adjustment face 24 be with handle with approaching the isolating direction of face, promptly on the orthogonal imaginary plane of the direction of haunting of the 2nd annulus 20 projection near shadow area with adjustment face 24, total area A 2 be the 2nd processing of projection on this imaginary plane with the 2nd processing of portion 20 with face 2 and separation total area with the shadow area of adjustment face 23.

Near with the front end and the front end that separates with adjustment face 23 of adjustment face 24, together being limited at cyclic the 2nd processing is on the front end of line L1 with the inner peripheral surface 25 of portion 20.Therefore, through determining to carry out the adjustment of equilibrium ratio near position with the cardinal extremity line L2 of adjustment face 24.

Promptly; In this embodiment; Be processed with fluidic in utilization and see off under the situation of pressure as opening force, handle with face 2 and separate total shadow area with adjustment face 23, can produce and the corresponding opening force of its area ratio greater than approaching shadow area with adjustment face 24 through making the 2nd.

For above-mentioned opening force, change above-mentioned line of balance, i.e. change is near with the area A 1 of adjustment face 24, thus, pressure that can be through being processed liquid, is hydrodynamicpressure adjustment.

Slipping plane real surface pressure P, be that the surface pressure that hydrodynamicpressure produced in the pressure of contact surface can be used computes.

P＝P1×(K-k)+Ps

In the formula, P1 represent to be processed liquid pressure, be hydrodynamicpressure, K representes above-mentioned equilibrium ratio, k representes the opening force coefficient, Ps representes spring and back pressure.

Adjust slipping plane real surface pressure P through the adjustment of this line of balance, make thus to handle to form desirable slight gap amount, form and be processed the film that liquid produces, make product become small, carry out uniform reaction treatment with face 1, between 2.

Usually, if two processing then can make product more small with the film fluidic less thick of 1,2 in face.On the contrary, big if film fluidic thickness becomes, to handle and become coarse, the treatment capacity of unit time increases.So, through the adjustment of above-mentioned slipping plane real surface pressure P, can adjust two and handle with face 1, interval between 2, can be when realizing desired homogeneous reaction the small product of acquisition.Below, claim that slipping plane real surface pressure P is surface pressure P.

Concluding should relation, under the thicker situation of above-mentioned product, can reduce equilibrium ratio, reduces surface pressure P, increases at interval, increases above-mentioned thickness.On the contrary, under the less situation of above-mentioned product, can increase equilibrium ratio, increase surface pressure P, reduce above-mentioned interval, reduce above-mentioned thickness.

Like this,, form,, can implement the adjustment of pressure of contact surface, can adjust and handle with the interval between face through the position of its line of balance near with adjustment face 24 as the part of pressure of contact surface imparting mechanism 4.

In the adjustment at above-mentioned interval, as stated, it is also conceivable that thrust pressure and the air pressure of air importing portion 44 through changing above-mentioned spring 43 carried out.And, hydrodynamicpressure promptly be processed liquid transfer pressure adjustment and become cf-adjustment the 1st handle with portion 10 to be the adjustment of the rotation of the 1st carriage 11, also to be important adjustment key element.

As stated; This device constitutes as follows; Promptly; Handle to handle with the 1st of portion's 20 rotations for the 2nd and handle with portion 10 with portion 20 and with respect to the 2nd, through obtaining the pressure equilibrium of sending into pressure, this rotary centrifugal force and pressure of contact surface that is processed liquid, two processing with face on the film fluid be scheduled to of formation.And at least one side of annulus is a floating structure, thus the location of absorbent core vibration etc., the danger of the caused abrasion of eliminating contact etc.

In the embodiment of this Figure 12 (B),, the same with the embodiment shown in Fig. 1 (A) for possessing above-mentioned adjustment with the structure beyond the face.

In addition, shown in figure 17 in the embodiment shown in Figure 12 (B), above-mentioned separation can be set with adjustment face 23.

As Figure 12 (B) and embodiment shown in Figure 17; Be provided with near under the situation with adjustment face 24; Through make near with the area A 1 of adjustment face 24 greater than above-mentioned area A 2; Thereby do not produce opening force, on the contrary, be applied to the predetermined pressure that is processed on the liquid and all work as pressure of contact surface.Also can carry out such setting, in this case,, can make two to handle with face 1,2 equilibriums through increasing other separating force.

Make the 2nd to handle with face 2 through above-mentioned area than having determined to act on from the 1st power handled with face 1 detaching direction, this masterpiece be from the suffered power of fluid with joint efforts.

In the above-mentioned embodiment, as stated, spring 43 is given uniform stress for slipping plane is promptly handled with face, and the installation number is The more the better.But this spring 43 also can that kind shown in figure 13, adopts monovolume type spring.It is that as shown in the figure, center and cyclic the 2nd are handled with portion's 20 concentric 1 spiral spring.

The 2nd handles with sealing to become the gastight mode between portion 20 and the 2nd carriage 21, and sealing can adopt well-known mechanism.

Shown in figure 14, be provided with the temperature adjustment in the 2nd carriage 21 with big envelope 46, this temperature adjustment is with big envelope 46 coolings or heat the 2nd processing with portion 20, its temperature of adjustable.And, the above-mentioned housing of 3 expressions of Figure 14, in this housing 3, the temperature regulation that also is provided with same purpose is with big envelope 35.

The temperature regulation of the 2nd carriage 21 is that water cycle is used the space with big envelope 46, and this water cycle is formed at the side of the annulus resettlement section 41 in the 2nd carriage 21 with the space, and be communicated to the 2nd carriage 21 outside passages 47,48 and be connected.The wherein direction temperature adjustment of passage 47,48 imports cooling with big envelope 46 or heats the medium of usefulness, and wherein the opposing party discharges this medium.

In addition, the temperature of housing 3 adjustment is through heating the passage of water or water coolant with big envelope 35, and the covering part 34 of its periphery through being arranged on covering shell 3 is arranged between the periphery and this covering part 34 of housing 3.

In this embodiment, the 2nd carriage 21 and housing 3 possess the said temperature adjustment and use big envelope, still, also such big envelope can be set in the 1st carriage 11.

As the part of pressure of contact surface imparting mechanism 4, except that above-mentioned, also cylinder mechanism shown in figure 15 7 can be set.

This cylinder mechanism 7 has: cylinder space portion 70, this cylinder space portion 70 are arranged in the 2nd carriage 21; Connection section 71, this connection section 71 connects cylinder space portion 70 and annulus resettlement section 41; Piston body 72, this piston body 72 are housed in the cylinder space portion 70 and through connection section 71 and the 2nd processing and are connected with portion 20; The 1st nozzle 73, the 1 nozzles 73 are connected with the top of cylinder space portion 70; The 2nd nozzle 74, the 2 nozzles 74 connect the bottom of cylinder space portion 70; Pushing body 75, this pushing body 75 are the clockwork spring between cylinder space portion 70 tops and piston body 72 etc.

Piston body 72 can slide up and down in cylinder space portion 70, and through this slip of piston body 72, the 2nd processing slides up and down with portion 20, thereby variable the 1st processing is handled with the interval between the face 2 with face 1 and the 2nd.

Though not shown, be specially, compressor equipressure source is connected with the 1st nozzle 73; Top through from the piston body 72 of the 1st nozzle 73 in cylinder space portion 70 applies air pressure; Be malleation, piston body 72 is slided downwards, make the 1st and the 2nd to handle with face 1, interval between 2 and narrow down.In addition; Though it is not shown; Compressor equipressure source is connected with the 2nd nozzle 74, applies air pressure through below, i.e. malleation from the piston body 72 of the 2nd nozzle 74 in cylinder space portion 70; Piston body 72 is slided to the top, thereby can make the 2nd to handle with portion 20 and move towards enlarging the direction that the 1st and the 2nd processing promptly opens with face 1, the direction at interval between 2.Like this, utilize the air pressure that obtains from nozzle 73,74, can adjust pressure of contact surface.

Even handle between the topmost with the top of portion 20 and annulus resettlement section 41 the 2nd in the annulus resettlement section 41 enough spaces are arranged; Through setting piston body 72 with the topmost 70a butt ground of cylinder space portion 70, the topmost 70a of this cylinder space portion 70 also defines two and handles with face 1, the upper limit of width at interval between 2.That is, the topmost 70a of piston body 72 and cylinder space portion 70 handles with face 1,2 is isolating and separates inhibition portion and play a role as suppressing two, in other words, handles as restriction two and to separate the mechanism of measuring with face 1, the maximum at interval between 2 and play a role.

In addition, even two handle with face 1,2 butt not each other, through with the foot 70b butt ground setting piston body 72 of cylinder space portion 70, the foot 70b of this cylinder space portion 70 defines two processing with face 1, the lower limit of interval width between 2.That is, the foot 70b of piston body 72 and cylinder space portion 70 handles with face 1,2 approaching playing a role near inhibition portion as suppressing two, more in other words, handles with face 1, the minimum at interval between 2 as restriction two and to separate the mechanism of measuring and play a role.

Like this; Limit the maximum and minimum separately amount at above-mentioned interval on one side; Can press the interval z1 of the topmost 70a that adjusts cylinder body 72 and cylinder space portion 70 on one side through the air of said nozzle 73,74, in other words, the interval z2 of the foot 70b of adjustment cylinder body 72 and cylinder space portion 70.

Nozzle 73,74 can be connected with another pressure source, also can be connected in a pressure source through switching or transferring.

And pressure source can be any device of supplying with malleation or supplying with negative pressure.Under negative pressure sources such as vacuum and situation that nozzle 73,74 is connected, form the action opposite with above-mentioned action.

Replace above-mentioned other pressure of contact surface imparting mechanisms 4 or as the part of above-mentioned pressure of contact surface imparting mechanism 4; Such cylinder mechanism 7 is set, according to viscosity that is processed liquid and characteristic thereof, the pressure of the pressure source that carries out being connected and the setting of z1, z2 at interval with nozzle 73,74; Make film fluidic thickness reach desired value; Impose shearing force, realize reaction uniformly, can generate small particle.Particularly,, can open and close, can improve and clean and the safety of sterilization in the pressure of cleaning and carry out sliding part steam sterilizing etc. the time through such cylinder mechanism 7.

Shown in Figure 16 (A)～(C), can, the 1st processing form groove shape recess 13...13 on handling with face 1 with the 1st of portion 10, and this groove shape recess 13...13 extends from the central side of the 1st processing with portion 10 toward the outer side, promptly extends diametrically.In this case; Shown in Figure 16 (A), recess 13...13 can be used as the 1st handle with face 1 on the part of bending or spiral extension implement, shown in Figure 16 (B); Also may be embodied as the groove that each recess 13 is bent into the L font; And shown in Figure 16 (C), recess 13...13 also can be embodied as the groove of linearly radial extension.

In addition, shown in Figure 16 (D), the recess 13 of preferred Figure 16 (A)～(C) with become towards the 1st handle the recess of deepening gradually with the central side of face 1 mode tilt and form.And the recess 13 of groove shape be except being the successive groove, the groove that also is interrupted.

Through forming such recess 13, have the effects such as minimizing, cavitation corrosion control and fluid bearing of increase or the thermal value of the output that reply is processed liquid.

In above-mentioned each embodiment shown in Figure 16, though being formed on the 1st, handles recess 13 with on the face 1, also can be embodied as and be formed on the 2nd processing with on the face 2, and, also can be embodied as and be formed on the 1st and the 2nd processing with on face 1,2 both sides.

On handling, be not provided with under the situation of above-mentioned recess 13 or tapering with face; Perhaps; Under the situation that they is offset to handle with the part of face, it is big to handle the device that the above-mentioned recess 13 of formation is compared in the influence that is processed liquid and applies with the surfaceness of face 1,2.So, under these circumstances,, just must reduce surfaceness if the particle that is processed liquid is diminished, promptly form slick.Particularly; Be under the situation of purpose with the homogeneous reaction; Handle surfaceness for it with face; Be under the situation of purpose to realize reaction uniformly and to obtain particulate, aforementioned minute surface, the face that has promptly applied mirror finish help realizing the crystallization of small monodispersed reaction product or separating out.

To embodiment shown in Figure 17, the structure beyond showing clearly especially is identical with Fig. 1 (A) or Figure 11 (C) illustrated embodiment at Figure 13.

In addition, in above-mentioned each embodiment, all sealings still, in addition, also can be embodied as in the housing, and only the 1st processing is sealed with the inboard that portion 10 and the 2nd handles with portion 20, and its outside is open.That is, up to through the 1st handle with face 1 and the 2nd processing with face 2 between till, stream is sealed, and is processed liquid and receives whole transfer pressures, still, after passing through, stream is opened, the liquid that is processed after the processing does not receive transfer pressure.

Give among the structure p1 at hydrodynamicpressure,, as stated, preferably use compressor to implement, still,, also can use other device to implement as long as can apply predetermined pressure to being processed liquid always as pressurizing device.For example, can promptly, utilize the deadweight that is processed liquid, through implementing like lower device always to being processed the device that liquid applies certain pressure.

Summarize the treatment unit in above-mentioned each embodiment; It is characterized by, apply predetermined pressure being processed liquid, receive this predetermined pressure be processed liquid institute mobile by the sealed fluid flow stream in; Connecting the 1st processing handles with 22 in face and can use face near isolating processing with face 1 and the 2nd at least; Apply and make two to handle with the approaching pressure of contact surface of face 1,2, handle with face 1 and the 2nd processing and relatively rotate with face 2 through making the 1st, utilization is processed the film fluid that is used to seal in the liquid generation mechanical seal; Opposite with mechanical seal (not being that the Film Flow body is used for sealing); This film fluid is handled with face 1 and the 2nd from the 1st is handled with spilling between the face 2, on the two sides 1, become film between 2 be processed between liquid also recovery of realization response processing.

Through above-mentioned epoch-making method, can handle with face 1, interval between 2 two and be adjusted into 1 μ m to 1mm, especially can carry out the adjustment of 1～10 μ.

In the above-described embodiment, constitute by the stream of sealed fluid flow in the device, the hydrodynamicpressure that is utilized in (the 1st be processed liquid) importing portion side setting of treatment unit is given structure p1, to being processed the liquid pressurization.

In addition, also can such hydrodynamicpressure give structure p1 and pressurize, but implement through the device that the stream that is processed liquid is opened.

Figure 18 to Figure 20 representes an embodiment of such treatment unit.In addition, in this embodiment, example have as treatment unit, from the material that generates, remove liquid, finally only guarantee the device of the function of solid (crystallization) as purpose.

Figure 18 (A) is the simple longitudinal diagram of treatment unit, and Figure 18 (B) is its local sectional view that enlarges.Figure 19 has the vertical view that the 1st of treatment unit shown in Figure 180 is handled with portion 101.Figure 20 is the partial longitudinal section that the 1st and the 2nd of above-mentioned treatment unit is handled with the major portion of portion 101,102.

Device shown in this Figure 18 to Figure 20 under atmospheric pressure, drops into the fluid as process object as stated, promptly is processed the fluid of the such process object thing of liquid or conveyance.

In addition, among Figure 18 (B) and Figure 20,, omitted the drawing of the 2nd d2 of importing portion (also can regard as section be in be not provided with the 2nd importing portion d2 position) for avoiding the numerous and diverse of drawing.

Shown in Figure 18 (A), this treatment unit possesses reaction unit G and drawdown pump Q.This reaction unit G possesses: handle with portion 101 as the 1st of rotating member; Keep 1st carriage 111 of this processing with portion 101; Handle with portion 102 as the 2nd of the member that is fixed with respect to housing; The fixing the 2nd handles the 2nd carriage 121 with portion 102; Suppress mechanism 103; Dynamic pressure generating mechanism 104 (Figure 19 (A)); Make the 1st to handle the driving part that together rotates with portion 101 and the 1st carriage 111; Housing 106; Supply with the 1st d1 of importing portion that (input) the 1st is processed liquid; Discharge fluidic discharge portion 108 to drawdown pump Q.Omit its diagram about driving part.

It is respectively the ring bodies with the shape that hollows out cylindrical center that above-mentioned the 1st processing is handled with portion 102 with portion 101 and the 2nd.Two handle with portion the 101, the 102nd, respectively two handle be cylinder with 101,102 in portion a bottom surface as the member of processing with face 110,120.

Above-mentioned processing has by the par of mirror ultrafinish with face 110,120.In this embodiment, the 2nd processing is tabular surfaces that whole face has all been implemented mirror ultrafinish with the processing of portion 102 with face 120.In addition, though make the 1st handle with the processing of portion 101 with the whole face of face 110 become with the 2nd processing with the identical tabular surface of portion 102,, shown in Figure 19 (A), in tabular surface, a plurality of groove 112...112 are arranged.This groove 112...112 handles with the 1st and uses the center of cylinder that portion 101 is to be central side, extends radially to the peripheral direction of cylinder.

The the relevant the above-mentioned the 1st and the 2nd handles with the processing of portion 101,102 mirror ultrafinish with face 110,120, and the preferred surface roughness is Ra0.01～1.0 μ m.More preferably this mirror ultrafinish reaches Ra 0.03～0.3 μ m.

The relevant material of handling with portion 101,102, employing hard and material that can mirror ultrafinish.Relevant this hardness of handling with portion 101,102 is preferably and ties up formula hardness at least more than 1500.And, preferably adopt little raw material of linear expansivity or the high raw material of thermal conduction.This be because, when handling, produce between the part and other parts of heat, if the difference of rate of expansion is bigger, will deform, thereby influence guaranteeing of appropriate intervals.

As the raw material of above-mentioned processing with portion 101,102, the especially preferred following material etc. that adopts: SIC is a silit, and its dimension formula hardness is 2000～2500; Surperficial DLC i.e. the SIC of type brill carbon coating, and wherein the dimension formula hardness of type brill carbon is 3000～4000; WC is a wolfram varbide, and its dimension formula hardness is 1800; The surface has applied WC, the ZrB of DLC coating ₂Or be the boron system pottery of representative with BTC, B4C, dimension formula hardness is 4000～5000.

Though housing 106 shown in Figure 180 has omitted the diagram of bottom, but for the cylindrical body at the end is arranged, the top is covered by above-mentioned the 2nd carriage 121.The 2nd carriage 121 is handled with portion 102 at its lower surface the fixing the above-mentioned the 2nd, is provided with the above-mentioned importing d1 of portion above it.The d1 of importing portion has hopper 170, and this hopper 170 is used for input fluid or object being treated from the outside.

Though not shown, above-mentioned driving part possesses propulsion source such as phonomoter and accepts power supply and the axle 50 that rotates from this propulsion source.

Shown in Figure 18 (A), the inside that axle 50 is disposed at housing 106 extends below up.And the upper end of axle 50 is provided with above-mentioned the 1st carriage 111.The 1st carriage 111 is to keep the device of the 1st processing with portion 101, through being arranged on the above-mentioned axle 50, makes the 1st processing handle corresponding with face 120 with the processing of portion 102 with the processing of portion 101 with face 110 and the 2nd.

The 1st carriage 111 is a cylinder, and surperficial above that central authorities are fixed with the 1st and handle with portion 101.The 1st processing is fixed with portion 101 and the 1st carriage 111 with becoming one, does not change its position with respect to the 1st carriage 111.

On the other hand, be formed with in the upper face center of the 2nd carriage 121 and accommodate the 2nd and handle and accommodate recess 124 with portion 102.

The above-mentioned recess 124 of accommodating has the cyclic transverse section.The 2nd handle with portion 102 with accommodate recess 124 concentric modes and be housed in columned accommodating in the recess 124.

This structure of accommodating recess 124 identical with the embodiment shown in Fig. 1 (A) (the 1st handles with portion's 101 corresponding the 1st annulus 10, the 1 carriages 111 corresponding the 1st carriages, 11, the 2 processing with portion's 102 corresponding the 2nd annulus 20, the 2 carriages 121 corresponding the 2nd carriages 21).

And the 2nd carriage 121 possesses the above-mentioned mechanism 103 of suppressing.Preferably suppress mechanism 103 and use elastomericss such as spring.It is corresponding with the pressure of contact surface imparting mechanism 4 of Fig. 1 (A) to suppress mechanism 103, adopts same spline structure.That is, suppress mechanism 103 pushing and the 2nd handle with the processing of portion 102 with the face of face 120 opposition sides, be the bottom surface, the 1st handle to being positioned at, the 2nd processing below promptly suppresses with each position of portion 102 equably with portion's 101 sides.

The internal diameter of on the other hand, accommodating recess 124 is greater than the external diameter of the 2nd processing with portion 102, thus; When disposing with one heart as stated; The 2nd handle with the periphery 102b of portion 102 with accommodate between the inner peripheral surface of recess 124, such shown in Figure 18 (B), setting interval t1.

Equally, such shown in Figure 18 (B) between the 2nd periphery handled with the inner peripheral surface 102a of portion 102 and the centre portions 22 of accommodating recess 124, setting interval t2.

Above-mentioned interval t1, t2 are respectively applied for absorbed oscillation and eccentric movement, and its size is set as follows, that is, and and more than or equal to the size that can guarantee to move and can form sealing.For example, use under the situation of diameter as 100mm to 400mm of portion 101 in the 1st processing, preferred this interval t1, t2 are respectively 0.05～0.3mm.

The 1st carriage 111 is fixed on the axle 50 integratedly, with axle 50 rotations.In addition, though not shown, utilize stopper, the 2nd processing can be with respect to 121 rotations of the 2nd carriage with portion 102.But; Handle with 110,120 in face two; In order to ensure handling necessary 0.1～10 micron interval; I.e. slight gap t shown in Figure 20 (B), the bottom surface of accommodating recess 124, be the top and towards the 2nd handle with the face of the top 124a of portion 102, promptly above between, be provided with interval t3.For this interval t3,, consider that axle 150 vibrates and extends and sets with above-mentioned interval.

As stated, through the setting of interval t1～t3, the 2nd handles with portion 102 and is not only handling with portion 101 near variable on the isolating direction Z1 with respect to the 1st, and is that direction z2 also is variable for its center, inclination of handling use face 120.

That is, in this embodiment, suppress mechanism 103 and constitute relocation mechanism with above-mentioned interval t1～t3, through this relocation mechanism, at least the 2 processing can change in the scope very in a small amount from several microns to the number millimeter with the center and the inclination of portion 102.Thus, absorb the core vibration of turning axle, surface vibration and the vibration that axle expansion, the 1st is handled with portion 101.

Handle the above-mentioned groove 112 that the processing with portion 101 is had with face 110 to the 1st, explain as follows in further detail.The rear end of groove 112 arrives the 1st inner peripheral surface 101a that handles with portion 101, and its front end is the extension of periphery side towards the 1st outside y that handles with portion 101.This groove 112 is shown in Figure 19 (A), and it is that the periphery side reduces gradually towards the 1st processing with the outside y of portion 101 that its cross-sectional area is handled with the center x side of portion 101 from cyclic the 1st.

It is that the periphery side reduces gradually towards the 1st processing with the outside y of portion 101 that the left and right sides face 112a of groove 112, the interval w1 of 112b handle with the center x side of portion 101 from the 1st.And the degree of depth w2 of groove 112 is shown in Figure 19 (B), and handling with the center x side of portion 101 from the 1st is that the periphery side reduces gradually towards the 1st processing with the outside y of portion 101.That is, to handle with the center x side of portion 101 from the 1st be that the periphery side shoals gradually towards the 1st processing with the outside y of portion 101 to the end 112c of groove 112.

Like this, all y is that the periphery side reduces gradually towards the outside for the width of groove 112 and the degree of depth, and y reduces gradually towards the outside thereby make its cross-sectional area.And the front end of groove 112 is that the y side becomes terminal point.That is, the front end of groove 112 is that the y side does not arrive the periphery 101b of the 1st processing with portion 101, between the front end and periphery 101b of groove 112, across outside tabular surface 113.This outside tabular surface 113 is for handling the part with face 110.

In this embodiment shown in Figure 19, the left and right sides face 112a of above-mentioned groove 112,112b and end 112c constitute the stream restrictions.This stream restrictions, the 1st is handled the par of handling with portion 102 with the par around the groove 112 of portion 101 and the 2nd and is constituted dynamic pressure generating mechanism 104.

But, also can only adopt said structure to the width of groove 112 and wherein arbitrary side of the degree of depth, reduce its sectional area.

Above-mentioned dynamic pressure generating mechanism 104 is through passing the fluid of two processing with 101,102 in portion when the 1st handles with portion's 101 rotations; Handle two and can guarantee desirable slight gap, make two processing produce reactive force on portion's 101,102 isolating directions with 101,102 in portion.Through the generation of above-mentioned dynamic pressure, can handle with 110,120 slight gap that produce 0.1～10 μ m of face two.Such slight gap, though can adjust selection according to the object of handling, still, preferred 1～6 μ m, more preferably 1～2 μ m.In this device, through above-mentioned slight gap, can realize impossible in the past homogeneous reaction, and generate particulate.

Groove 112...112 can implement as follows, that is, and and the x side y extension toward the outer side from the center as the crow flies.But in this embodiment, shown in Figure 19 (A), for the 1st sense of rotation r that handles with portion 101, the mode that the center x side of groove 112 is gone ahead of the rest with the outside y than groove 112, promptly to be positioned at the mode in the place ahead crooked, makes groove 112 extensions.

Extend agley through above-mentioned groove 112...112, can more effectively produce separating force through dynamic pressure generating mechanism 104.

Below, the action of this device is described.

Drop into from hopper 170, be processed the hollow bulb that liquid R handles with portion 102 through cyclic the 2nd through the 1st of the 1st d1 of importing portion.Receiving the 1st handles and to be processed liquid R with the 1st of the cf-that rotation produced of portion 101 and to get into two processing with portion 101, between 102; The 1st of rotation handle with the processing of portion 101 with face 110 and the 2nd processing with the processing of portion 102 with face 120 between; React uniformly and the generation of fine particle is handled; Subsequently, come the outside of two processing, be expelled to drawdown pump Q side through discharge portion 108 with portion 101,102.Below, be processed liquid R with the 1st as required and only be called fluid R.

In above-mentioned, enter into ring-type the 2nd and handle liquid R with the hollow bulb of portion 102 shown in Figure 20 (A), at first, get into the groove 112 of the 1st processing of rotation with portion 101.On the other hand, though by mirror ultrafinish, handle with face 110,120 as two of par and also to keep its resistance to air loss through gases such as air or nitrogen.So even rotated the action of centrifugal force that is produced, under this state, liquid can not get into by two processing of suppressing mechanism's 103 pressings with face 110, between 120 from groove 112.But liquid R and above-mentioned two sides 112a, 112b and the end 112c of the groove 112 that forms as the stream restrictions collide at leisure, produce to act on to make to separate two processing with the dynamic pressure on face 110, the 120 isolating directions.Shown in Figure 20 (B), thus, liquid R is exuded on the tabular surface from groove 112, can guarantee that two processing are the gap with the slight gap t of 110,120 in face.In addition, between the tabular surface after the above-mentioned mirror ultrafinish, react uniformly and the generation of fine particle is handled.And the bending of above-mentioned groove 112 convection cell effect more effectively cf-more effectively produces above-mentioned dynamic pressure.

As stated, this treatment unit through dynamic pressure with suppress the equilibrium of forces that suppresses that mechanism 103 produced, can promptly handle with face 110, guarantee between 120 that small and uniform interval is the gap at two minute surfaces.And through said structure, the ultra micro that this slight gap can form below the 1 μ m is closely-spaced.

In addition; Through adopting above-mentioned relocation mechanism; The localized automatic adjustment of handling with 110,120 in face becomes possibility; For because of the rotation and the physical deformation of the caused each several part that generates heat, can suppress to handle deviation with the interval of each position of 110,120 in face, can keep the above-mentioned slight gap of this each position.

Moreover in the above-described embodiment, relocation mechanism is the mechanism that only on the 2nd carriage 121, is provided with.In addition, can also replace the 2nd carriage 121, on the 1st carriage 111, relocation mechanism is set also, perhaps on the 1st carriage 111 and the 2nd carriage 121, relocation mechanism is set all.

Figure 21 to Figure 23 representes other embodiments of above-mentioned groove 112.

As Figure 21 (A) (B) shown in, groove 112 can possess smooth wall 112d at its front end as the part of stream restrictions.And, in this embodiment, on end 112c, between the 1st wall 112d and inner peripheral surface 101a, being provided with step 112e, this step 112e also constitutes the part of stream restrictions.

As Figure 22 (A) (B) shown in, groove 112 can be embodied as, and has the 112f...112f of branch portion of a plurality of bifurcateds, each 112f of has the stream restrictions through dwindling its width.

In these embodiments,, identical with the embodiment shown in Fig. 1 (A), Figure 11 (C), Figure 18 to Figure 20 particularly for the structure that does not illustrate.

And, in above-mentioned each embodiment,, handle toward the outer side from the 1st with the inboard of portion 101 for the width of groove 112 and one of them side of the degree of depth, reduce its size gradually, constitute the stream restrictions thus.In addition, shown in Figure 23 (A) and Figure 23 (B), through the not width and the degree of depth of variable grooves 112 end face 112f is set in groove 112, the end face 112f of this groove 112 also can form the stream restrictions.Shown in the embodiment that Figure 19, Figure 21 and Figure 22 represent, dynamic pressure produces to be carried out as follows, promptly; The width and the degree of depth through groove 112 change as aforementioned, make the end of groove 112 and two sides become the scarp, thus; This scarp becomes with respect to the fluidic compression zone, produces dynamic pressure.On the other hand, (B) in the illustrated embodiment, the end face of groove 112 becomes with respect to the fluidic compression zone, produces dynamic pressure at Figure 23 (A).

In addition, under the situation of this Figure 23 (A) shown in (B), one of them side's the size of width and the degree of depth of groove 112 is reduced gradually.

Moreover, about the structure of groove 112, be not limited to above-mentioned Figure 19, Figure 21 to structure shown in Figure 23, also can be embodied as the structure of stream restrictions with other shapes.

For example, to structure shown in Figure 23, groove 112 is not penetrated into the outside of the 1st processing with portion 101 at Figure 19, Figure 21.That is, between the periphery and groove 112 of the 1st processing, there is outside tabular surface 113 with portion 101.But, be not limited to above-mentioned embodiment, as long as can produce above-mentioned dynamic pressure, groove 112 also can arrive the periphery side of the 1st processing with portion 101.

For example, handle under the situation with portion 101, shown in dotted line, can be embodied as, sectional area is formed on the tabular surface 113 of the outside less than the part at other positions of groove 112 at the 1st shown in Figure 23 (B).

In addition, as stated, form groove 112 with the mode that reduces sectional area from the inboard laterally gradually, part (terminal) the formation minimum sectional area that the arrival the 1st of groove 112 is handled with portion's 101 peripheries gets final product (not shown).But for producing dynamic pressure effectively, to shown in Figure 23, preferred groove 112 does not penetrate the 1st and handles with portion's 101 periphery sides like Figure 19, Figure 21.

At this, above-mentioned Figure 18 is summarized to various embodiments shown in Figure 23.

This treatment unit make have smooth processing with the rotating member of face with to have smooth processing equally relative with one heart with face with the stationary member smooth processing separately of face; Under the rotation of rotating member; Supply with by reaction raw materials from stationary member peristome separately on one side; On one side between the relative plane treatment of two members is with face, carrying out reaction treatment, in this treatment unit, is not mechanically to adjust the interval; But booster body is set in rotating member; Can keep through the pressure of its generation at interval, and form the slight gap of 1～6 μ m that the interval adjustment institute of machinery can not reach, the micro ability of generation particle and the homogenizing ability of reaction are significantly improved.

Promptly; In this treatment unit; Rotating member and stationary member have smooth processing at its peripheral part and use face; This smooth processing has the sealing function on the face with mask, and the high-speed rotary treatment unit can be provided, and it is that hydrostatic, fluid dynamic power are hydrodynamic force or aerostatics-aerodynamic power that this high-speed rotary treatment unit produces fluidstatic power.Above-mentioned power makes the small interval of generation between the above-mentioned trim, and the reaction treating device with following function can be provided, that is, and and noncontact, machine security, height micro and reaction homogenizing.Can form the essential factor of this slight gap, one is the rotating speed of rotating member, and another is the input side and the pressure difference of discharging side of object being treated (fluid).The situation that the pressure imparting mechanism is not set in the input side promptly under atmospheric pressure drops under the situation of object being treated (fluid), because no pressure difference must only rely on the rotating speed of rotating member to produce the separation between trim.Known fluid dynamic power or aerodynamic power that Here it is.

In Figure 18 (A) shown device; Though be expressed as the discharge portion that drawdown pump Q is connected above-mentioned reaction unit G, also can as noted earlier, be embodied as, housing 106 is not set; And drawdown pump Q is not set; But shown in Figure 24 (A),, in this container T, set reaction unit G with the container T of treatment unit as decompression usefulness.

In this case; Be decompressed to vacuum in the container T or near the state of vacuum through making; The object being treated that generates among the reaction unit G is ejected in the container T with nebulizing, runs into the object being treated that the inwall of container T flows down through recovery, or; Recovery with respect to the above-mentioned object being treated that flows down as gas (steam) material separated, that be full of container T top, the object after can obtaining to handle.

In addition, under the situation of using drawdown pump Q, shown in Figure 24 (B), treatment unit G connects gastight container T via drawdown pump Q, and in this container T, the object being treated after the processing forms vaporific, can carry out the separation or the extraction of object.

In addition, shown in Figure 24 (C), drawdown pump Q is directly connected in container T, in this container T, connects drawdown pump Q and divides the discharge portion of the fluid R that opens with drawdown pump Q, can carry out the separation of object.In this case, for gasification portion, liquid R (aqueous portion) is depressurized pump Q and attracts to assemble, and discharges through discharge portion, and does not discharge from vaporization portion.

In above-mentioned each embodiment, show like lower device, that is, and with the 1st and the 2 two kind be processed liquid and import from the 2nd carriage 21,121 and the 2nd annulus 20,102 respectively, make it the device that mixes and react.

Below, describe in order to other embodiments that device imports being processed liquid.

Shown in Fig. 1 (B), can be embodied as, in the treatment unit shown in Fig. 1 (A), the 3rd d3 of importing portion is set, be processed liquid with the 3rd and import two and handle with face 1, between 2, make it be processed liquid and likewise be processed liquid and mix and react with the 1st with the 2nd.

The 3rd d3 of importing portion is processed liquid blended the 3rd liquid to handling with face 1,2 supplies with the 1st.In this embodiment, the 3rd d3 of importing portion is provided in a side of the fluid channel of the 2nd annulus 20 inside, and the one of which end is handled with face 2 upper sheds the 2nd, and its other end connects the 3rd fluid supply unit p3.

In the 3rd fluid supply unit p3, can adopt compressor, other pump.

The 3rd d3 of importing portion compares with the peristome of the 2nd d2 of importing portion with the peristome on the face 2 in the 2nd processing and is positioned at the outside of the 1st processing with the rotation center of face 1.That is, the 2nd handle with face 2 on, the peristome of the 3rd d3 of importing portion than the opening of the 2nd d2 of importing portion in the downstream side.Between the peristome of the peristome of the 3rd d3 of importing portion and the 2nd d2 of importing portion, devices spaced apart on the inward-outward direction of the diameter of the 2nd annulus 20.

In this Fig. 1 (B) shown device, the formation beyond the 3rd d3 of importing portion is identical with the embodiment shown in Fig. 1 (A).And, below this Fig. 1 (B) reaches, among Fig. 1 (C) of explanation, Fig. 1 (D), Fig. 2～Figure 11,, omitted housing 3 for avoiding the numerous and diverse of drawing.And, Fig. 9 (B) (C), Figure 10, Figure 11 (A) (B) in, described the part of housing 3.

In addition, shown in Fig. 1 (C), can be embodied as; In treatment unit shown in Fig. 1 (B); The 4th d4 of importing portion is set, is processed liquid with the 4th and imports two and handle, make it be processed liquid and likewise be processed liquid and mix and react with the 1st with the 2nd and the 3rd with face 1, between 2.

The 4th d4 of importing portion is processed liquid blended the 4th fluid to handling with face 1,2 supplies with the 1st.In this embodiment, the 4th d4 of importing portion is provided in a side of the fluid channel of the 2nd annulus 20 inside, and the one of which end is handled with face 2 upper sheds the 2nd, and its other end connects the 4th fluid supply unit p4.

In the 4th fluid supply unit p4, can adopt compressor, other pump.

The 4th d4 of importing portion handles with the peristome on the face 2 than the 3rd d3 of importing portion opening in the outside of the 1st processing with the rotation center of face 1 the 2nd.That is, the 2nd handle with face 2 on, the peristome of the 4th d4 of importing portion than the opening of the 3rd d3 of importing portion in the downstream side.

For the structure beyond the 4th d4 of importing portion of Fig. 1 (C) shown device, identical with the embodiment shown in Fig. 1 (B).

And, though not shown, also can be embodied as, the importing portions more than 5 such as the 5th importing portion, the 6th importing portion are set in addition, make respectively to be processed that liquid mixes and reaction more than 5 kinds.

In addition, shown in Fig. 1 (D), can be embodied as, in the device of Fig. 1 (A), the 1st d1 of importing portion and the 2nd d2 of importing portion that are arranged on the 2nd carriage 21 likewise are arranged on the 2nd processing with on the face 2, it is arranged on the 2nd carriage 21 to replace.In this case, the 2nd handle with face 2 on, the peristome of the 1st d1 of importing portion is a upstream side than the central side that the 2nd d2 of importing portion is positioned at rotation also.

In above-mentioned Fig. 1 (D) shown device, the peristome of the 2nd d2 of importing portion is configured in the 2nd of the 2nd annulus 20 with the peristome of the 3rd d3 of importing portion and handles with on the face 2.But the peristome of importing portion is not limited to above-mentionedly be configured with face with respect to handling.Particularly, can be shown in Fig. 2 (A), the peristome of the 2nd d2 of importing portion is arranged on the 2nd annulus 20 inner peripheral surface, with the 2nd handle and implement with face 2 adjoining positions.In this Fig. 2 (A) shown device; Though the peristome of the 3rd d3 of importing portion likewise is configured in the 2nd with Fig. 1 (B) shown device and handles with on the face 2; But; Also can be configured in the inboard of above-mentioned the 2nd processing through peristome, promptly handle with face 2 adjoining positions, directly import to processing with on the face thereby be processed liquid with the 2nd with the 2nd with the 2nd d2 of importing portion with face 2.

As stated; Be arranged on the 2nd carriage 21 through peristome the 1st d1 of importing portion; The peristome of the 2nd d2 of importing portion is configured in the inboard of the 2nd processing with face 2, promptly handles with face 2 adjoining positions (in this case, above-mentioned the 3rd d3 of importing portion being set not necessarily) with the 2nd; Thereby; Particularly, can the liquid that is processed that import from the 1st d1 of importing portion be imported two processing with face 1, between 2 with the liquid that is processed that imports from the 2nd d2 of importing portion under nonreactive state making under a plurality of situation that are processed liquid reaction, and can make both in two processing with face 1, react for the first time between 2.Therefore, said structure is particularly suitable for using the reactive high situation that is processed liquid.

What explain is, above-mentioned " adjacency " is not limited in following situation, that is, the mode that the peristome of the 2nd d2 of importing portion is contacted with the inner side surface with the 2nd annulus 20 shown in Fig. 2 (A) is provided with.From the distance of the peristome of the 2nd annulus 20 to the 2nd d2 of importing portion is that following degree gets final product; That is, a plurality of be processed liquid be imported into two handle with face 1, between 2 before, by the degree of mixing or reacting fully; For example, also can be arranged on position near the 2nd annulus 20 of the 2nd carriage 21.And, also can the peristome of the 2nd d2 of importing portion be arranged on the 1st annulus 10 or the 1st carriage 11 sides.

In addition, in above-mentioned Fig. 1 (B) shown device, between the peristome of the peristome of the 3rd d3 of importing portion and the 2nd d2 of importing portion; Inward-outward direction devices spaced apart at the diameter of the 2nd annulus 20; But also can be embodied as, shown in Fig. 2 (B), above-mentioned interval is not set; Be processed liquid with the 2nd and the 3rd and import two processing, make two fluids interflow at once with face 1, between 2.Above-mentioned Fig. 2 of Object Selection (B) shown device according to handling gets final product.

In addition; In above-mentioned Fig. 1 (D) shown device, between the peristome of the peristome of the 1st d1 of importing portion and the 2nd d2 of importing portion, separated at interval in the inward-outward direction of the 2nd annulus 20 diameters; But also can be embodied as; This interval is not set, imports two processing with face 1, between 2, make two fluids interflow at once and be processed liquid with the 1st and the 2nd.Configuration according to the such peristome of the Object Selection of handling gets final product.

In above-mentioned Fig. 1 (B) and Fig. 1 (C) illustrated embodiment; The 2nd handle with face 2 on, the peristome of the 3rd d3 of importing portion is configured in the downstream side of the peristome of the 2nd d2 of importing portion, in other words; On the inward-outward direction of the diameter of the 2nd annulus 20, be configured in the outside of the peristome of the 2nd d2 of importing portion.In addition, shown in Fig. 2 (C) and Fig. 3 (A), can the 2nd handle with face 2 on, the peristome of the 3rd d3 of importing portion is disposed on the Zhou Fangxiang r0 of the 2nd annulus 20 implements with the different position of the 2nd d2 of importing portion peristome.In Fig. 3, m1 representes that the peristome of the 1st d1 of importing portion is the 1st peristome, and m2 representes that the peristome of the 2nd d2 of importing portion is the 2nd peristome, and m3 representes that the peristome of the 3rd d3 of importing portion is the 3rd peristome, and r1 is the inward-outward direction of circle diameter.

In addition; The 1st d1 of importing portion is being arranged under the situation on the 2nd annulus; Also can be shown in Fig. 2 (D), the 2nd handle with face 2 on, the Zhou Fangxiang that the peristome of the 1st d1 of importing portion is disposed at the 2nd annulus 20 implements with the different position of peristome of the 2nd d2 of importing portion.

In above-mentioned Fig. 2 (C) shown device, the processing of the 2nd annulus 20 with face 2 on, the peristome of 2 importing portions is configured in the different positions of Zhou Fangxiang r0; But; Also can be embodied as, shown in Fig. 3 (B), dispose the peristome of 3 importing portions at the different positions of the Zhou Fangxiang of annulus r0; Or shown in Fig. 3 (C), dispose the peristome of 4 importing portions at the different positions of the Zhou Fangxiang of annulus r0.In addition, Fig. 3 (B) (C) in, m4 representes the peristome of the 4th importing portion, in Fig. 3 (C), m5 representes the peristome of the 5th importing portion.And, though not shown, also can be embodied as, dispose the peristome of the importing portion more than 5 at the different positions of the Zhou Fangxiang of annulus r0.

(D) and in Fig. 3 (A)～(C) shown device, the 2nd importing portion to the 5 lead-in portions can not import the different liquids that is processed, and promptly the 2nd, the 3rd, the 4th, the 5th are processed liquid at above-mentioned Fig. 2 (B).On the other hand, can be embodied as, the peristome m2～m5 from the 2nd～the 5th, with all similar, promptly the 2nd be processed liquid and import processing with between the face.Though not shown, in this case, can be embodied as, 5 importing portions of the 2nd importing portion to the are in the annulus internal communication, and are connected to a fluid supply unit, i.e. the 2nd fluid supply unit p2.

In addition; Can implement with lower device through combination, that is, the device of the peristome of a plurality of importing portion is set at the different positions of the Zhou Fangxiang of annulus r0; And, be the device that the different positions of the inward-outward direction r1 of diameter is provided with the peristome of a plurality of importing portion in the circle diameter direction.

For example; Shown in Fig. 3 (D); The 2nd be provided with 8 importing portions on handling with face 2 peristome m2～m9; 4 m2～m5 wherein be arranged on annulus Zhou Fangxiang r0 different positions and be arranged on the same position on the diametric(al) r1, other 4 m6～m9 be arranged on annulus Zhou Fangxiang r0 different positions and be arranged on the same position on the diametric(al) r1.And these other peristome m6～m9 is configured in the diametric outside of above-mentioned 4 peristome m2～m5 on diametric(al) r1.And, though the peristome in this outside can be arranged at position identical with the peristome of inboard on the circumferential direction r0 of annulus respectively, still, considering the rotation of annulus, also can be embodied as, shown in Fig. 3 (D), be arranged on the different positions of the Zhou Fangxiang r0 of annulus.In addition, in this case, peristome is not limited to configuration and the quantity shown in Fig. 3 (D).

For example, shown in Fig. 3 (E), also can the peristome in the direction outside, footpath be configured in polygonal vertex position, i.e. tetragonal vertex position under this situation, the peristome that the footpath direction is inboard is configured on this polygonal limit.Certainly, also can adopt other configuration.

In addition; Peristome beyond the 1st peristome m1 all with the 2nd be processed liquid import handle with the situation between face under; May be embodied as; Import each the 2nd be processed liquid this peristome be not on the Zhou Fangxiang r0 that handles with face, to scatter, but shown in Fig. 3 (F), formation successive peristome on Zhou Fangxiang r0.

Moreover the object according to handling shown in Fig. 4 (A), can be embodied as, in Fig. 1 (A) shown device, and the middle body 22 that the 2nd d2 of importing portion and the 1st d1 of importing portion that are arranged on the 2nd annulus 20 likewise are arranged on the 2nd carriage 21.In this case, with respect to the peristome of the 1st d1 of importing portion at the center that is positioned at the 2nd annulus 20, the opening of the 2nd d2 of importing portion is in its outside, and devices spaced apart.And, shown in Fig. 4 (B), can be embodied as, in Fig. 4 (A) shown device, the 3rd d3 of importing portion is arranged at the 2nd annulus 20.Shown in Fig. 4 (C); Can be embodied as, in Fig. 4 (A) shown device, not be provided with between the peristome of the peristome of the 1st d1 of importing portion and the 2nd d2 of importing portion at interval; After being processed liquid and importing the inboard space of the 2nd annulus 20 the 1st and the 2nd, make two fluids interflow immediately.In addition, the object according to handling can be embodied as, and identical with the 2nd d2 of importing portion in Fig. 4 (A) shown device shown in Fig. 4 (D), the 3rd d3 of importing portion also is arranged on the 2nd carriage 21.Though not shown, still, also can be embodied as, the importing portion more than 4 is set on the 2nd carriage 21.

And the object according to handling shown in Fig. 5 (A), can be embodied as, and in the device shown in Fig. 4 (D), the 4th d4 of importing portion is set on the 2nd annulus 20, is processed liquid with the 4th and imports two processing with face 1, between 2.

Shown in Fig. 5 (B), can be embodied as, in Fig. 1 (A) shown device, the 2nd d2 of importing portion is arranged at the 1st annulus 10, the 1st have the 2nd d2 of importing portion on handling with face 1 peristome.

Shown in Fig. 5 (C); Can be embodied as, in Fig. 5 (B) shown device, the 1st annulus 10 is provided with the 3rd d3 of importing portion; The 1st handle with face 1 on, the peristome of the 3rd d3 of importing portion is configured in peristome with the 2nd d2 of importing portion different position on the Zhou Fangxiang of the 1st annulus 10.

Shown in Fig. 5 (D), can be embodied as, in Fig. 5 (B) shown device, be substituted in the 1st d1 of importing portion be set on the 2nd carriage 21, the 1st d1 of importing portion is set on the 2nd annulus 20, the 2nd dispose the 1st d1 of importing portion on handling with face 2 peristome.In this case, two peristomes of the 1st and the 2nd d1 of importing portion, d2 are configured in same position on the inward-outward direction of circle diameter.

In addition, shown in Fig. 6 (A), also can be embodied as, in Fig. 1 (A) shown device, the peristome that the 3rd d3 of importing portion is arranged at the 1st annulus 10, the 3 d3 of importing portion is arranged on the 1st processing with on the face 1.In this case, two peristomes of the 2nd and the 3rd d2 of importing portion, d3 are configured in same position on the inward-outward direction of circle diameter.But, also can above-mentioned two peristomes be disposed at different positions on the inward-outward direction of the diameter of annulus.

In Fig. 5 (C) shown device; Though two peristomes with the 3rd and the 3rd d2 of importing portion, d3 are set on the inward-outward direction of the diameter of the 1st annulus 10 in identical position, be to be arranged on different positions on the sense of rotation at the Zhou Fangxiang of the 1st annulus 10 simultaneously; Also can be embodied as; In this device, shown in Fig. 6 (B), two peristomes of the 2nd and the 3rd d2 of importing portion, d3 are arranged on different positions on the inward-outward direction of the diameter of the 1st annulus 10.In this case, can be embodied as, shown in Fig. 6 (B); Between two peristomes of the 2nd and the 3rd d2 of importing portion, d3, devices spaced apart in advance on the inward-outward direction of the diameter of the 1st annulus 10, in addition; Though it is not shown; Also can be embodied as, not separate this interval, make the 2nd to be processed liquid and the 3rd and to be processed liquid interflow immediately.

In addition, can be embodied as, shown in Fig. 6 (C), be substituted in the 1st d1 of importing portion is set on the 2nd carriage 21, but, the 1st d1 of importing portion is arranged on the 1st annulus 10 with the 2nd d2 of importing portion.In this case, in the 1st handled with face 1, the peristome of the 1st d1 of importing portion was arranged on the upstream side (inboard of the inward-outward direction of the diameter of the 1st annulus 10) of the peristome of the 2nd d2 of importing portion.Between the peristome of the peristome of the 1st d1 of importing portion and the 2nd d2 of importing portion, devices spaced apart in advance on the inward-outward direction of the diameter of the 1st annulus 10.But, though not shown, also can not separate this compartment of terrain and implement.

In addition, can be embodied as, shown in Fig. 6 (D), in the 1st of Fig. 6 (C) shown device is handled with face 1,, dispose the peristome of the 1st d1 of importing portion and the 2nd d2 of importing portion respectively at the different positions of the Zhou Fangxiang of the 1st annulus 10.

In addition, though not shown, in the embodiment of Fig. 6 (C) shown in (D); Can be embodied as, the importing portion more than 3 is set on the 1st annulus 10, at the different positions of the 2nd processing with the Zhou Fangxiang on the face 2; Perhaps, the different positions in the inward-outward direction of circle diameter disposes each peristome.For example, also can in the 1st handles with face 1, adopt the configuration of peristome shown in Fig. 3 (B)～Fig. 3 (F) that the 2nd processing adopted in face 2.

Shown in Fig. 7 (A), can be embodied as, in Fig. 1 (A) shown device, be substituted in the 2nd d2 of importing portion is set on the 2nd annulus 20, the 2nd importing portion is set on the 1st carriage 11.In this case, in the position that is surrounded by the 1st annulus 10 above the 1st carriage 11, preferably at the peristome of center configuration the 2nd d2 of importing portion of the hub of the rotation of the 1st annulus 10.

Shown in Fig. 7 (B), in the embodiment shown in Fig. 7 (A), can the 3rd d3 of importing portion be arranged at the 2nd annulus 20, the peristome of the 3rd d3 of importing portion is configured in the 2nd handles with on the face 2.

In addition, shown in Fig. 7 (C), can be embodied as, be substituted in the 1st d1 of importing portion is set on the 2nd carriage 21, the 1st d1 of importing portion is set on the 1st carriage 11.In this case, in the position that is surrounded by the 1st annulus 10 above the 1st carriage 11, the preferred peristome of configuration the 1st d1 of importing portion on the hub of the rotation of the 1st annulus 10.In addition, as shown in the figure in this case, can the 2nd d2 of importing portion be arranged at the 1st annulus 10, its peristome is configured in the 1st handles with on the face 1.In addition, though not shown, in this case,, dispose its peristome on handling with face 2 the 2nd can the 2nd d2 of importing portion is arranged at the 2nd annulus 20.

And, shown in Fig. 7 (D), can be embodied as, the 2nd d2 of importing portion shown in Fig. 7 (C) is arranged on the 1st carriage 11 with the 1st d1 of importing portion.In this case, in the position that is surrounded by the 1st annulus 10 above the 1st carriage 11, dispose the peristome of the 2nd d2 of importing portion.In addition, in this case, in Fig. 7 (C), also can be the 2nd d2 of importing portion that is provided with on the 2nd annulus 20 as the 3rd d3 of importing portion.

In each embodiment of above-mentioned Fig. 1～shown in Figure 7, the 1st carriage 11 and the 1st annulus 10 are with respect to the 2nd carriage 21 and 20 rotations of the 2nd annulus.In addition, shown in Fig. 8 (A), can be embodied as, in Fig. 1 (A) shown device, acceptance is set from the revolving force of rotary driving part and the turning axle 51 that rotates on the 2nd carriage 21, the 2nd carriage 21 is rotated on the direction opposite with the 1st carriage 11.Rotary driving part also can be arranged with the device branch that the turning axle that makes the 1st carriage 11 50 rotates, and perhaps conduct is implemented like lower device, that is, this device is accepted power through Poewr transmission mechanisms such as gears from the driving part that the turning axle 50 that makes the 1st carriage 11 rotates.In this case, the 2nd carriage 21 forms with above-mentioned housing split ground, and likewise rotatably is housed in this housing with the 1st carriage 11.

And, shown in Fig. 8 (B), can be embodied as, same with the device of Fig. 7 (B) in Fig. 8 (A) shown device, the 2nd d2 of importing portion is set on the 1st carriage 11, to be substituted in the 2nd d2 of importing portion is set on the 2nd annulus 20.

In addition, though not shown, also can be embodied as, in Fig. 8 (B) shown device, the 2nd d2 of importing portion is set on the 2nd carriage 21, to be substituted in the 2nd d2 of importing portion is set on the 1st carriage 11.In this case, the 2nd d2 of importing portion is identical with the device of Fig. 4 (A).Shown in Fig. 8 (C), also can be embodied as, in Fig. 8 (B) shown device, the 3rd d3 of importing portion is set on the 2nd annulus 20, the peristome of the d3 of this importing portion is arranged on the 2nd handles with on the face 2.

And, shown in Fig. 8 (D), also can be embodied as, do not make 11 rotations of the 1st carriage, only rotate the 2nd carriage 21.Though not shown, also can be embodied as, in the device of Fig. 1 (B)～shown in Figure 7, the 2nd carriage 21 and the 1st carriage 11 all rotate, or only the 2nd carriage 21 rotates separately.

Shown in Fig. 9 (A), the 2nd handles and to use portion 20 be annulus, and the 1st to handle with portion 10 be not annulus, but with other the 1st carriage 11 of embodiment same, directly have members that turning axle 50 also rotates.In this case, the 1st processing is handled with face 1 as the 1st with the upper surface of portion 10, this processing is not a ring-type with face, does not promptly possess hollow space, forms the same tabular surface.And same with the device of Fig. 1 (A) in Fig. 9 (A) shown device, the 2nd annulus 20 is provided with the 2nd d2 of importing portion, and its peristome is configured in the 2nd and handles with on the face 2.

Shown in Fig. 9 (B); Can be embodied as; In Fig. 9 (A) shown device, the 2nd carriage 21 is independent with housing 3, between housing 3 and the 2nd carriage 21; Pressure of contact surface imparting mechanism 4 is set, and this pressure of contact surface imparting mechanism 4 is to make the 2nd carriage 21 the 1st handle with portion's 10 approaching isolating elastomericss etc. to what be provided with the 2nd annulus 20.In this case, shown in Fig. 9 (C), the 2nd processing does not form annulus with portion 20, as the member that is equivalent to above-mentioned the 2nd carriage 21, can the lower surface of this member be handled with face 2 as the 2nd.And, shown in Figure 10 (A), can be embodied as; In Fig. 9 (C) shown device; The 1st processing does not form annulus with portion 10 yet, and (B) shown device is the same with Fig. 9 (A), in other embodiment; Handle with portion 10 as the 1st at the position that will be equivalent to the 1st carriage 11, and its upper surface is handled with face 1 as the 1st.

In above-mentioned each embodiment; At least the 1 to be processed liquid be to handle from the 1st that to handle with portion 20 with portion 10 and the 2nd be the central part supply of the 1st annulus 10 and the 2nd annulus 20; Through utilizing other the processing that liquid carries out that is processed; After promptly mixing and reacting, be discharged to the outside of the inward-outward direction of its diameter.

In addition, shown in Figure 10 (B), also can be embodied as, supply with the 1st from the outside of the 1st annulus 10 and the 2nd annulus 20 towards the inboard and be processed liquid.In this case; As shown in the figure, the outside with housing 3 sealing the 1st carriages 11 and the 2nd carriage 21 directly is arranged at this housing 3 with the 1st d1 of importing portion; In the inboard of housing, the peristome of this importing portion is configured in the corresponding position of docking location with two annulus 10,20.And, in the device of Fig. 1 (A),, promptly become the position at center of the 1st annulus 10 of the 1st carriage 11 in the position that is provided with the 1st d1 of importing portion, be provided with discharge portion 36.In addition, clip the hub of the rotation of carriage, dispose the peristome of the 2nd d2 of importing portion at the opposition side of this peristome of housing.But; The peristome of the 2nd d2 of importing portion is identical with the peristome of the 1st d1 of importing portion; So long as get final product, and be not defined as the opposition side of the peristome that is formed on the 1st d1 of importing portion of above-mentioned that kind at the inboard of housing and the corresponding position of docking location that is configured in two annulus 10,20.

The discharge portion 36 of the product after the processing is set in advance.In this case, the outside of the diameter of two annulus 10,20 becomes upstream side, and the inboard of two annulus 10,20 becomes the downstream side.

Shown in Figure 10 (C), can be embodied as, in Figure 10 (B) shown device, change the position of the 2nd d2 of importing portion of the sidepiece that is arranged at housing 3, it is arranged at the 1st annulus 10, and its peristome is configured in the 1st processing with on the face 1.In this case, shown in Figure 10 (D), can be embodied as; The 1st processing does not form annulus with portion 10, and is identical with Fig. 9 (A), Fig. 9 (B) and Figure 10 (A) shown device, in other embodiment; Handle with portion 10 as the 1st at the position that will be equivalent to the 1st carriage 11, its upper surface is handled with face 1 as the 1st, and; The 2nd d2 of importing portion is arranged at the 1st handles, its peristome is arranged on the 1st handles with on the face 1 with in the portion 10.

Shown in Figure 11 (A), can be embodied as, in Figure 10 (D) shown device, the 2nd processing does not form annulus with portion 20, and in other embodiment, the member that will be equivalent to the 2nd carriage 21 is handled with portion 20 as the 2nd, and its lower surface is handled with face 2 as the 2nd.And, may be embodied as, with the 2nd handle with portion 20 as with housing 3 member independently, between housing 3 and the 2nd processing are with portion 20, with Fig. 9 (B) (C) and Figure 10 (A) shown device identical, be provided with pressure of contact surface imparting mechanism 4.

In addition, shown in Figure 11 (B), also can be embodied as, the 2nd d2 of importing portion of Figure 11 (A) shown device as the 3rd d3 of importing portion, is provided with the 2nd d2 of importing portion in addition.In this case, in the 2nd handled with face 2, the peristome of the peristome of the 2nd d2 of importing portion being compared the 3rd d3 of importing portion was configured in the downstream side.

Above-mentioned each device shown in Figure 4, Fig. 5 (A), Fig. 7 (A) (B) (D), Fig. 8 (B) (C) shown device be that other are processed liquid and handle with face 1, are processed the device that liquid collaborates with the 1st before between 2 arriving, be not suitable for crystallization and the reaction of separating out material fast.But the material slow for speed of response then can adopt such device.

About being fit to the treatment unit of the related method working of an invention of the application, be summarized as follows.

As stated, this treatment unit has: hydrodynamicpressure is given structure, and this hydrodynamicpressure is given structure and applied predetermined pressure to being processed liquid; The 1st processing is handled with portion 10 and the 2nd and is used portion with 20 at least 2 processing of portion; The 1st handles with what portion 10 was arranged on this predetermined pressure and is processed the liquid mobile by in the sealed fluid flow stream, and the 2nd handle can relatively approaching separation with respect to the 1st handling part 10 with portion 20; The 1st handles to handle with face 1 and the 2nd and uses face with 2 at least 2 processing of face, and the 1st processing is arranged on opposed facing position in above-mentioned processing in portion 10,20 with face with 2 at least 2 processing of face with face 1 and the 2nd processing; Rotary drive mechanism, this rotary drive mechanism make the 1st processing relatively rotate with portion 20 with portion 10 and the 2nd processing; Handle with face 1, between 2 two, carry out at least 2 kinds and be processed the mixing of liquid and the processing of reaction.In the 1st processing is handled with portion 20 with portion 10 and the 2nd; At least the 2 processing has load face with portion 20; And at least a portion of this load face is handled by the 2nd and is constituted with face 2; Load face receives hydrodynamicpressure and gives the pressure that structure is given at least one side who is processed liquid, on the 2nd processing is handled with face 1 isolating direction with face 2 from the 1st, produces the power that moves it.And; In this device, between can handling with face 2 with face 1 and the 2nd, flow through the liquid that is processed that receives above-mentioned pressure effect near the 1st processing that separates and relatively rotate; Thus; Respectively be processed liquid and pass through two processing with face 1, between 2 while the film fluid that forms predetermined thickness, thereby, be processed at this and produce desired response between liquid.

In addition, in this treatment unit, the preferred device that possesses buffer gear that adopts, this buffer gear are adjusted the 1st and are handled the little vibration and the location of handling with at least one side of face 2 with face 1 and the 2nd.

In addition; In this treatment unit; The preferred structure that possesses the displacement adjustment mechanism that adopts; This displacement adjustment mechanism adjust the 1st handle with face 1 and the 2nd handle with side of face 2 or both sides, by the axial displacement that causes such as wearing and tearing, can keep two processing with face 1, film fluidic thickness between 2.

And, in this treatment unit, giving structure as above-mentioned hydrodynamicpressure, can adopt to apply certain pressurizing devices such as compressor of sending into pressure to being processed liquid.

And above-mentioned pressurizing device adopts the device of the adjustment of the increase and decrease that can send into pressure.This pressurizing device needs and can the pressure of setting be kept certain, still, handles the parameter with the interval between face as adjustment, also is necessary and can adjusts.

In addition, in this treatment unit, can adopt to have the structure of separating inhibition portion, this separations inhibition portion stipulates that the above-mentioned the 1st handles with face 1 and the 2nd and handle with the largest interval between the face 2, and two processing more than the inhibition largest interval are with face 1,2 separation.

In addition, in this treatment unit, can adopt the structure that has near inhibition portion, stipulate that near inhibition portion the above-mentioned the 1st handles with face 1 and the 2nd and handle with the minimum interval between the face 2, following two processing in inhibition minimum interval are approaching with face 1,2.

And, in this treatment unit, can adopt following structure, that is, the 1st processing is handled with face 2 both sides towards mutually reciprocal mutually direction rotation with face 1 and the 2nd.

In addition, in this treatment unit, can adopt the structure of the big envelope with temperature adjustment usefulness, the big envelope of this temperature adjustment usefulness is adjusted above-mentioned the 1st processing and is handled with a side of face 2 or both sides' temperature with face 1 and the 2nd.

In addition, in this treatment unit, preferably adopt following structure, that is, above-mentioned the 1st processing is handled with face 1 and the 2nd and has been carried out mirror finish with a side of face 2 or at least a portion of both sides.

In this treatment unit, can adopt following structure, that is, the above-mentioned the 1st handles the side or the both sides that handle with face 2 with face 1 and the 2nd has recess.

And; In this treatment unit; The following structure of preferred employing, that is, and as the opposing party's who is processed the liquid reaction who makes a side the supply mean that is processed liquid; Have the importing road independently other with a side the passage that is processed liquid; Handle on any at least side who handles with face with face 1 and the 2nd the above-mentioned the 1st, have the peristome that communicates with above-mentioned other importing road, can be with the opposing party's who sends here from this other importing road the liquid that is processed that liquid imports an above-mentioned side that is processed.

In addition, the treatment unit of enforcement the application invention has: hydrodynamicpressure is given structure, and this hydrodynamicpressure is given structure and applied predetermined pressure to being processed liquid; The 1st processing is used face with face 1 and the 2nd processing with the approaching isolating processing that 2 at least 2 in face can be relative, and the 1st processing is handled with face 1 and the 2nd and is connected by the sealed fluid flow stream with the liquid mobile that is processed of this predetermined pressure with face 2; Pressure of contact surface imparting mechanism, this pressure of contact surface imparting mechanism are handled two and are applied pressure of contact surface with face 1,2; Rotary drive mechanism, this rotary drive mechanism make the 1st processing rotate relatively with face 2 with face 1 and the 2nd processing; Owing to have said structure, handle with face 1, between 2 two, carry out at least 2 kinds the reaction treatment that is processed liquid; The treatment unit of implementing the application's invention can adopt following structure, that is, counterrotating the 1st processing is handled with between the face 2 with face 1 and the 2nd when being applied in pressure of contact surface; Flow through and give at least a kind that structure exerts pressure from hydrodynamicpressure and be processed liquid, and, be processed liquid through flowing through another kind; Giving structure from hydrodynamicpressure is applied in above-mentioned a kind of pressure and is processed the film fluid that liquid forms predetermined thickness on one side; Handle with face 1, between 2 through two on one side, at this moment, it is mixed that this another kind is processed liquid; Be processed between liquid, desired response is taking place.

The little vibration of adjustment and localized buffer gear or displacement adjustment mechanism that this pressure of contact surface imparting mechanism can constitute in the said apparatus are implemented.

And then the treatment unit as implementing the application's invention can adopt with lower device, that is, this device has: 2 kinds of liquids that are processed that are processed at least one side in the liquid that the 1st importing portion, the 1st importing portion will react import this device; Hydrodynamicpressure is given structure p, and this hydrodynamicpressure is given structure p and is connected in the 1st importing portion and exerts pressure to this side's the liquid that is processed; 2 kinds of liquids that are processed that are processed other sides at least in the liquid that the 2nd importing portion, the 2nd importing portion will react import this device; Portion is used at least 2 processing, and these at least 2 are handled use portion is that the liquid mobile that is processed that is arranged at this side is handled with portion 10 and can be handled with portion 20 near the isolating the 2nd relatively with portion 10 with respect to the 1st by the 1st processing of sealed fluid flow stream; The 1st processing is handled with face 1 and the 2nd and is used face with 2 at least 2 processing of face, and the 1st handles the position that in these handle with portion 10,20, is arranged on mutual subtend with face 1 and the 2nd processing with face 2; Carriage 21, this carriage 21 is handled the mode of exposing with face 2 with the 2nd and is accommodated the 2nd processing with portion 20; Rotary drive mechanism, this rotary drive mechanism make the 1st processing rotate relatively with portion 20 with portion 10 and the 2nd processing; Pressure of contact surface imparting mechanism 4, these pressure of contact surface imparting mechanism 4 pushings the 2nd are handled with portion 20, the 2nd processing is handled with respect to the 1st with face 2 be in crimping or approaching state with face 1; Handle with face 1, between 2 two; Be processed the reaction treatment between liquid, above-mentioned carriage 21 is movable bodys not, in the peristome with above-mentioned the 1st importing portion; Exert one's influence to handling with face 1, interval between 2; The 1st handles the peristome that has above-mentioned the 2nd importing portion with at least one side of portion 10 and the 2nd importing portion 20, and the 2nd processing uses portion 20 to be ring bodies, and the 2nd handles with face 2 with respect to carriage 21 slips; Handle with face 1 near separating with the 1st; The 2nd processing has load face with portion 20, and load face receives hydrodynamicpressure and gives the effect that structure p puts on the pressure that is processed liquid, makes the 2nd to handle the power that moves it with face 1 isolating direction generation from the 1st processing with face 2; At least a portion of above-mentioned load face is handled by the 2nd and is constituted with face 2; Can near separate and the counterrotating the 1st handle with face 1 and the 2nd processing with face 2 between, the liquid that is processed that has been applied in a side of pressure passes through, simultaneously; The liquid that is processed through with an other side supplies to two processing with face 1, between 2; Two be processed liquid while the film fluid that forms predetermined thickness from two handling, pass through between 2 with face 1, through in be processed the liquid mixing, thereby promotion is processed the desired response between liquid; What pressure of contact surface through pressure of contact surface imparting mechanism 4 and hydrodynamicpressure were given the structure hydrodynamicpressure that p1 is applied makes two to handle with face 1, isolating equilibrium of forces between 2, handles with face 1, the film fluidic slight gap of the above-mentioned predetermined thickness of maintenance generation between 2 two.

This treatment unit also can be embodied as, and the 2nd importing portion also is connected in other hydrodynamicpressure with the 1st importing portion that is connected in the samely and gives structure, thereby pressurized.And; Also can be embodied as; Do not given the structure pressurization from the liquid that is processed that the 2nd importing portion imports by other hydrodynamicpressure; But by the vacuum suction that produces in the 2nd importing portion and supply to two and handle with face 1, between 2, above-mentioned negative pressure is to be produced by the hydrodynamicpressure that is processed liquid that the 1st importing portion is imported.And, also can be embodied as, this opposing party's the liquid that is processed moves through its deadweight in the 2nd importing portion, promptly flows to the below from the top, handles with face 1, between 2 thereby be supplied to.

As stated, be not limited only to the peristome of the 1st importing portion is arranged on the 2nd carriage, also can this peristome of the 1st importing portion be arranged on the 1st carriage, the peristome of above-mentioned the 1st importing portion becomes a side the supplying opening in device that is processed liquid.In addition, also can be embodied as, this peristome of the 1st importing portion is formed on two at least one sides of handling with face.But; Under following situation; That is,, be necessary to supply with and import processing earlier with under face 1, the situation that is processed liquid between 2 from the 1st importing portion according to reaction; Which processing no matter the peristome of the 2nd importing portion of the supplying opening in formation the opposing party's the device that is processed liquid be positioned at is used face, and the peristome of comparing above-mentioned the 1st importing portion all must be configured in the position in downstream side.

And the treatment unit as being used to implement the application's invention can adopt following device.

This treatment unit has: a plurality of importing portions, and what this a plurality of lead-in portion did not import reaction is processed liquid more than 2 kinds; Hydrodynamicpressure is given structure p, and this hydrodynamicpressure is given structure this at least a of liquid that be processed more than 2 kinds is exerted pressure; Portion is used at least 2 processing, these at least 2 processing with portion be arranged on this be processed the liquid mobile by the 1st in the sealed fluid flow stream handle with portion 10 with can handle with portion's 10 approaching isolating the 2nd processing with portion 20 with respect to the 1st; The 1st processing is handled with 22 processing of face with face 1 and the 2nd be arranged on these processing with in portion 10,20 opposed facing position with face 1 and the 2nd processing with face 2 with face 1,2, the 1 processing at least; Rotary drive mechanism, this rotary drive mechanism make the 1st processing rotate relatively with portion 20 with portion 10 and the 2nd processing; Handle with face 1, between 2 two; Be processed the reaction treatment between liquid; In the 1st processing was handled with portion 20 with portion 10 and the 2nd, at least the 2 processing had load face with portion 20, and; At least a portion of this load face is handled by the 2nd and is constituted with face 2; Load face receives hydrodynamicpressure and gives structure and put on the pressure that is processed liquid, makes the 2nd to handle with face 2 and handle the power that moves it with the generation of face 1 detaching direction from the 1st, and; The 2nd handle with portion 20 have towards with the 2nd handle approaching with face 2 opposition sides with adjustment face 24; Be applied to the predetermined pressure that is processed on the liquid near receiving, make the 2nd to handle with face 2 and handle the power that generation moves it on the direction approaching with face 1 to the 1st, through above-mentioned approaching area ratio near the shadow area of detaching direction near the shadow area of detaching direction and above-mentioned load face with adjustment face 24 with adjustment aspect 24; Determine the 2nd to handle the power that moves to detaching direction with face 1 with respect to the 1st processing with face 2; This masterpiece is for from being processed making a concerted effort of the suffered total pressure of liquid, and what be endowed pressure is processed liquid can be near separating and the counterrotating the 1st handle with face 1 and the 2nd processing and pass through between with face 2, is processed other that react in the liquid at this and is processed liquid and between two processing are with face, mixes; Blended is processed liquid and passes through two processing with face 1, between 2 while the film fluid that forms predetermined thickness, thereby in the reaction product through obtaining in handling with the process between face to hope.

In addition, the treatment process to the application's invention is summarized as follows.This treatment process is to give the 1st to be processed the predetermined pressure of liquid; With the 1st handle with face 1 and the 2nd handle with 2 at least 2 in face can approaching relatively isolating processing with face be connected in the above-mentioned predetermined pressure of acceptance be processed that liquid flows and by the sealed fluid flow stream; Apply and make two to handle with the approaching pressure of contact surface of face 1,2; The 1st processing is handled with face 1 and the 2nd relatively rotates with face 2; And will be processed liquid and import this processing with face 1, between 2, through with the above-mentioned stream that separates, will and this be processed that liquid reacts the 2nd be processed liquid and import above-mentioned processing with face 1, between 2; Make two to be processed the liquid reaction; To the major general put on the 1st be processed liquid above-mentioned predetermined pressure as making two to handle with face 1,2 isolating separating forces, reach balance via processing with face 1, the liquid that is processed between 2 through making this separating force and above-mentioned pressure of contact surface, thus two processing with face 1, keep predetermined slight gap between 2; Being processed liquid becomes the film fluid of pre-determined thickness and passes through two processing with face 1, between 2; This carry out equably in through process two be processed liquid reaction, under situation, crystallizable or separate out the desired response product with the reaction of separating out.

Below, other embodiments that the application is invented describe.Figure 25 is can be near isolating, at least one side with respect to the processing of the opposing party rotation simpleization sectional view with the reaction unit of face chien shih reactant reaction.(A) of Figure 26 is the simpleization vertical view that the 1st of device shown in Figure 25 is handled with face, (B) is the enlarged view of the processing of device shown in Figure 25 with the major portion of face.(A) of Figure 27 is the sectional view of the 2nd introduction channel, (B) is to be used to explain the enlarged view of the processing of the 2nd introduction channel with the major portion of face.

In Figure 25, U representes the top, and S representes the below.

In Figure 26 (A), Figure 27 (B), R representes sense of rotation.

In Figure 27 (B), C representes the direction (radial direction) of cf-.

This device; The liquid that is processed as above-mentioned explanation; Use at least 2 kinds of fluids, wherein at least a kind of fluid contains at least a kind of reactant, can near isolating each other set in the face of ground and processing that at least one side rotates with respect to the opposing party with face between; Make above-mentioned each fluid interflow and form the film fluid, in this film fluid, make above-mentioned reactant reaction.

Shown in figure 25, this device has: the 1st carriage 11, the 2nd carriage 21, the hydrodynamicpressure of configuration given structure P, and pressure of contact surface imparting mechanism above the 1st carriage 11.The pressure of contact surface imparting mechanism is made up of spring 43 and air importing portion 44.

On the 1st carriage 11, being provided with the 1st handles with portion 10 and turning axle 50.The 1st handles with portion 10 is the ring bodies that are called the cooperation ring, has by the 1st of mirror finish and handle with face 1.Turning axle 50 is fixed on the center of the 1st carriage 11 with the mounting block 81 of bolt etc., and the rotating driving device 82 (rotary drive mechanism) of its rear end and phonomoter etc. is connected, and the motivating force of rotating driving device 82 is passed to the 1st carriage 11 and makes 11 rotations of the 1st carriage.The 1st processing becomes one with above-mentioned the 1st carriage 11 with portion 10 and is rotated.

On the top of the 1st carriage 11, be provided with and can accommodate the resettlement section of the 1st processing with portion 10, through embedding in this resettlement section, the 1st processing is installed on the 1st carriage 11 with portion 10.And the 1st processing is fixing through spline pin 83 with portion 10, thereby with respect to 11 rotations of the 1st carriage.But, also can replace spline pin 83, fix with methods such as shrink-on, thereby it is not rotated.

Above-mentioned the 1st processing is exposed from the 1st carriage 11 with face 1, towards the 2nd carriage 21.The 1st material handled with face adopts: ceramic or burn till metal; Wear resisting steel; Other metals have been implemented the material of solidification treatment; Perhaps, apply, coat, be electroplate with the material of mechanically resistant material.

On the 2nd carriage 21, be provided with: the 2nd handles with portion 20; From handling inboard fluidic the 1st d1 of importing portion that imports with portion; Spring 43 as the pressure of contact surface imparting mechanism; And, air importing portion 44.

The 2nd to handle with portion 20 are the ring bodies that are called compression ring, have by what mirror finish was crossed the 2nd to handle with face 2 and load face 23 (below be called separate) with adjustment face 23, this load face 23 be positioned at the 2nd processing with the inboard of face 2 and with the 2nd processing with face 2 adjacency.As shown in the figure, this separation uses adjustment face 23 to be the scarp.To the 2nd handle that the mirror finish that is applied with face 2 adopts and the 1st processing with the identical method of face 1.In addition, the 2nd handle that material with portion 20 adopts and the 1st processing with the identical material of portion 10.Separate inner peripheral surface 25 adjacency of handling with portion 20 with adjustment face 23 and cyclic the 2nd.

In the bottom (bottom) of the 2nd carriage 21, form annulus resettlement section 41, O shape annulus and the 2nd is handled and is housed in simultaneously in this annulus resettlement section 41 with portion 20.And, do not accommodated rotatably with respect to the 2nd carriage 21 with portion 20 through 84, the 2 processing of spline pin.Above-mentioned the 2nd processing is exposed from the 2nd carriage 21 with face 2.Under this state, the 2nd processing is handled with the 1st processing of portion 10 with face 2 and the 1st and is faced with face 1.

The annulus resettlement section 41 that the 2nd carriage 21 is had be accommodate the 2nd annulus 20, mainly be the recess of handling with the position of the opposition side of face 2 sides, when overlooking, be formation cyclic groove.

Annulus resettlement section 41 forms with the mode greater than the size of the 2nd annulus 20, between itself and the 2nd annulus 20, has sufficient interval, accommodates the 2nd annulus 20.

Through this at interval, the 2nd handle with portion 20 with can be in the axial of resettlement section 41 and in the mode with this direction displacement that axially intersects is housed in this annulus resettlement section 41.And the 2nd processing is accommodated with the mode of displacement as follows with portion 20, that is, with respect to annulus resettlement section 41, make the 2nd processing not parallel with the direction of principal axis of above-mentioned annulus resettlement section 41 with the medullary ray (direction of principal axis) of portion 20.

At least in the annulus resettlement section 41 of the 2nd carriage 21, be provided with as the spring of handling with portion's elastic pressing part 43.Spring 43 is handled with portion 20 the 2nd and is suppressed with portion 10 towards the 1st processing.And, as other the method for suppressing, also can use the pressing mechanism of air importing portion pressure such as 44 air supplies such as grade or other hydrodynamicpressures, the 2nd processing that the 2nd carriage 21 keeps is suppressed with the direction of portion 10 towards handling near the 1st with portion 20.

Pressure of contact surface imparting mechanisms such as spring 43 and air importing portion 44 are handled the 2nd processing equably with each position (handling each position with face) of the Zhou Fangxiang of portion 20 and are suppressed with portion 10 towards the 1st.

Central authorities at the 2nd carriage 21 are provided with above-mentioned the 1st d1 of importing portion; At first be imported in the following space by the fluid of force feed with portion's outer circumferential side towards handling from the 1st d1 of importing portion; That is what, the 2nd carriage 21 kept the 2nd handles with portion the 20, the 1st and handles with portion 10 and keep in the space that the 1st processing enclosed with the 1st carriage 11 of portion 10.And; Make the 2nd handle overcome suppressing of elastic pressing part with portion 20 and from the 1st processing with portion's 10 isolating directions on; On the load face 23 that in the 2nd handles with portion 20, is provided with, receive from hydrodynamicpressure and give the above-mentioned fluidic transfer pressure (supply pressure) that structure P is produced.

In other positions, be schematic illustration, though only load face 23 is explained; But, correct, as Figure 29 (A) (B) shown in; With above-mentioned load face 23; With after state during the 2nd of channel form recess 13 handles with portion 20 corresponding direction of principal axis projection planes, the part 23X that is not provided with above-mentioned load face 23 also as load face, is received hydrodynamicpressure and gives the above-mentioned fluidic transfer pressure (supply pressure) that structure P is produced.

Also can be embodied as, above-mentioned load face 23 is not set.In this case; Shown in Figure 26 (A); Also can use to handle with face 1 and rotate the processing that obtains with the importing effect that is processed liquid (Micropump effect) between face through the 1st; Above-mentioned the 1st processing has channel form recess 13 with face 1, and this channel form recess 13 has the function of pressure of contact surface imparting mechanism.The Micropump effect here is meant; Through the rotation of the 1st processing with face 1; Fluid in the recess has speed ground and advances to the peripheral direction front end of recess, and then, the fluid of sending into the front end of recess 13 receives the pressure from the interior Zhou Fangxiang of recess 13 in addition; Final formation makes processing upward pressure with the isolating side of face, has simultaneously fluid is imported processing with the effect between face.And, even under non-rotary situation, be arranged at the 1st processing and finally act on the 2nd processing with on the face 2 with the fluid pressures in the recess 13 of face 1, the 2nd handles with face 2 as the load face that acts on the separation side.

For being arranged at the recess of handling with face 13, can implement its degree of depth corresponding to the fluidic physicals that contains reactant and reaction product, with respect to handling with in the horizontal direction the total area, bar number of face, reaching shape.

And, can be embodied as, above-mentioned load face 23 together is arranged in the device with above-mentioned recess 13.

The degree of depth of this recess 13 is 1 μ m～50 μ m, is preferably 3 μ m～20 μ m, is arranged on above-mentioned processing with the recess on the face; Accounting for the use face of processing integral body with respect to the use face of the processing total area in the horizontal direction is 5%～50%; Be preferably 15%～25%, its number is 3～50, is preferably 8～24; Be shaped as in the shape of handling with bending on the face or spiral extension, perhaps for being the shape of L font bending.And the degree of depth has the gradient, and the zone from the HV zone to LV even contain under the solid situation at the fluid that utilizes the Micropump effect to import, also can import fluid stable ground and handle with between the face.And, promptly handle with the face inboard in the importing side, be arranged between each recess of handling with the recess on the face 13 and can be connected to each other, also can break off each other.

As stated, load face 23 is the scarp.This scarp (load face 23) forms as follows, that is, with the flow direction that is processed liquid be benchmark upstream-side-end, with the processing that is provided with recess 13 with the processing of portion with the relative axial distance of face, bigger than the same distance of end of downstream side.And preferably the flow direction to be processed liquid on this scarp is that the end of downstream side of benchmark is arranged on the direction of principal axis projection plane of above-mentioned recess 13.

Specifically, shown in Figure 28 (A), the end of downstream side 60 on above-mentioned scarp (load face 23) is arranged on the direction of principal axis projection plane of above-mentioned recess 13.Angle θ 1 with face 2 is handled in 0.1 ° to 85 ° scope, more preferably in 10 ° to 55 ° scope, further preferably in 15 ° to 45 ° scope with respect to the 2nd in preferred above-mentioned scarp.Characteristic before this angle θ 1 can handle according to object being treated suitably changes.And; The end of downstream side 60 on above-mentioned scarp is arranged on in the lower area; That is, handle the position that upstream-side-end 13-b with the recess 13 of face 1 setting leaves 0.01mm from side downstream and the 1st and begin, leave to upstream side and end of downstream side 13-c in the zone till the position of 0.5mm.More preferably, be arranged on in the lower area, that is, the position of leaving 0.05mm from side and upstream-side-end 13-b downstream begins, and leaves to upstream side and end of downstream side 13-c in the zone till the position of 1.0mm.Identical with the angle on above-mentioned scarp, for the position of this end of downstream side 60, characteristic that can corresponding object being treated suitably changes.And shown in Figure 28 (B), scarp (load face 23) can be embodied as arc.Thus, can carry out the importing of object being treated more equably.

Recess 13 also can be embodied as the form of being interrupted except that as above-mentioned, connecting.Under the situation of being interrupted, the recess 13 that is interrupted, the 1st handle with face 1 in the upstream-side-end of all sides form above-mentioned 13-b; Equally, the 1st processing forms above-mentioned 13-c with the upstream-side-end of the most peripheral side of face 1.

In addition, handle with on the face 1, load face 23 is formed on the 2nd handles with on the face 2 though in above-mentioned explanation, recess 13 is formed on the 1st; But, on the contrary, also can be embodied as; Recess 13 is formed on the 2nd handles, load face 23 is formed on the 1st handles with on the face 1 with on the face 2.

In addition; Handle with 2 liang of sides of face with face 1 and the 2nd through recess 13 being formed on the 1st processing; And recess 13 and load face 23 alternately are arranged on each handle on the Zhou Fangxiang with face 1,2, thereby the 1st handle can be relative with the load face 23 of formation on the face 2 with the recess 13 that forms on the face 1 and the 2nd processing; Simultaneously, the 1st processing can be relative with the recess 13 that forms on the face 2 with load face 23 that forms on the face 1 and the 2nd processing.

In handling, also can implement the groove different with recess 13 with face.Concrete instance is shown in Figure 16 (F) and Figure 16 (G), at radial outside (Figure 16 (F)) or the radially inner side (Figure 16 (G)) than recess 13, can implement the new recess 14 of radial extension.It helps wanting to prolong the situation handling with the residence time between face, and the fluidic situation of handling high viscosity materials.

Moreover, about the groove different, shape, area, bar number, the degree of depth are not done special the qualification with recess 13.Can implement this groove according to purpose.

In the above-mentioned the 2nd handles with portion 20, with being imported into above-mentioned processing independent mutually with the fluidic stream of face, formation has the 2nd importing portion d2 of the processing of passing to the peristome d20 between face.

Be specially, the 2nd d2 of importing portion handles the importing direction that the peristome d20 with face 2 begins from the above-mentioned the 2nd and handles with the elevation angle (θ 1) inclination of face 2 to be scheduled to respect to the 2nd shown in Figure 27 (A).This elevation angle (θ 1) is set to greater than 0 degree less than 90 degree, and, be under the situation of rapidly reaction in speed of response, preferably be set to below 1 degree above 45 spends.

In addition, shown in Figure 27 (B), handle importing direction that the peristome d20 with face 2 begins along having directivity in above-mentioned the 2nd plane of processing with face 2 from the above-mentioned the 2nd.The processing that the 2nd fluidic imports direction use the composition of the radial direction of face be from the center away from outer direction, and and the relative composition of fluidic sense of rotation between the processing use face that rotates is forward.In other words, with the radial direction through peristome d20, promptly the line segment of outer direction has predetermined angle (θ 2) from this reference line g to sense of rotation R as reference line g.

This elevation angle (θ 1) is set to greater than 0 degree to be spent less than 90, and, under the situation of the fast reaction of speed of response, preferably be set to below above 45 degree of 1 degree.

In addition, angle (θ 2) also is set at greater than 0 degree to be spent less than 90, towards the netting twine part of Figure 27 (B), discharges from peristome d20.And under the situation of the fast reaction of speed of response, preferably this angle (θ 2) is set at smaller angle, and under the situation of the slow reaction of speed of response, preferably this angle (θ 2) is set at than wide-angle.In addition, this angle can be implemented with the various condition changes such as speed of rotation of face according to fluidic kind, speed of response, viscosity, processing.

The bore of peristome d20 is preferably 0.2 μ m～3000 μ m, more preferably 10 μ m～1000 μ m.And when peristome d20 bore was big, the diameter of the 2nd d2 of importing portion was 0.2 μ m～3000 μ m; Most preferably be 10 μ m～1000 μ m; In fact, do not influence under the fluidic mobile situation at the diameter of peristome d20, the diameter of the 2nd d2 of importing portion is arranged in this scope and gets final product.In addition, requiring under the situation of rectilinear propagation property, and requiring preferably to make the variations such as shape of peristome d20 under the diffusible situation, can implement with the various condition changes such as speed of rotation of face according to fluidic kind, speed of response, viscosity, processing.

And; The peristome d20 of above-mentioned other stream can be arranged on the outside diameter of following point; That is, utilize and to be arranged on the point that the 1st flow direction when handling Micropump effect with the recess of face 1 and importing is transformed to the streamlined flow direction of spirrillum that between processing is with face, forms.That is, among Figure 26 (B), preferably since the 1st handle the recess that use face 1 is provided with processing use face diameter to outermost, to radial outside apart from n as 0.5mm more than.And,, preferably be arranged on the concentric(al) circles in that same fluid is provided with under the situation of a plurality of peristomes.In addition, different fluid is being provided with under the situation of a plurality of peristomes, preferably is being arranged on the different concentric(al) circles of radius.As reacting, the original so reaction that should not react simultaneously of A+B+C → F and reactant are not contacted, thereby avoid reacting the problem of not carrying out effectively with the order of (1) A+B → C (2) C+D → E.

In addition, can be embodied as, above-mentioned processing is immersed in the fluid with portion, will between above-mentioned processing is with face, react the fluid that obtains and directly put in the liquid of handling with the portion outside or the gas beyond the air.

And, also can ultrasonic energy be applied to just from handling with between face or on the object being treated of processing with the face discharge.

Then; Between handling with face 2 with face 1 and the 2nd in above-mentioned the 1st processing; Promptly between handling, produce temperature head with face, the 1st handle with portion 10 and the 2nd processing with portion 20 one of them is provided with thermoregulative mechanism (thermoregulation mechanism) J1, J2 at least, be explained below.

Though this thermoregulative mechanism does not have special qualification,, under with the situation that is cooled to purpose, cooling end is arranged at processing with portion 10,20.Be specially, will be installed on as the cooling element that temperature adjustment can electric or chemically be carried out cooling effect with the pipe arrangement that frozen water or various refrigerant passed through of medium or Peltier element etc. and handle with portion 10,20.

Under with the situation that is heated to be purpose, in handling, be provided with the heating part with portion 10,20.Be specially, will be installed on as the Heating element that temperature adjustment can electric or chemically be carried out heat effect with the pipe arrangement that steam or various heating agent passed through of medium or hot plate etc. and handle with portion 10,20.

In addition, also can be provided with in the annulus resettlement section can with handle the resettlement section that the new temperature adjustment that directly contacts with portion is used with medium.Thus, utilize the thermal conduction of handling with portion, can handle temperature adjustment with face.And, cooling element or Heating element imbedded handle, or imbed cold and hot matchmaker through with passage and make temperature adjustment pass through this passage, thereby can carry out temperature adjustment with face from the inboard to processing with medium (cold and hot matchmaker) with in the portion 10,20 and energising.And thermoregulative mechanism J1 shown in Figure 25, J2 are the one of which example, are arranged on each and handle the pipe arrangement (big envelope) that passes through with medium with portion's 10,20 inner temperature adjustments.

Utilize above-mentioned thermoregulative mechanism J1, J2, the processing that makes a side is used surface temperature with the processing that the temperature of face is higher than the opposing party, between handling with face, produces temperature head.For example, the 1st processing is heated to 60 ℃ with above-mentioned arbitrary method with portion 10, and the 2nd processing is heated to 15 ℃ with above-mentioned arbitrary method with portion 20.At this moment, import processing and be changed to 15 ℃ with face 2 from 60 ℃ towards the 2nd processing with face 1 from the 1st processing with the fluidic temperature between face.That is, this is handled with the fluid between face and produces thermograde.And processing because this thermograde begins convection current, produces with respect to handle flowing with the vertical direction of face with the fluid between face.And above-mentioned " flowing of vertical direction " is meant in the mobile direction composition, contains the composition of vertical above-mentioned processing with face at least.

Even handle under the situation about handling with face 2 rotations with face 1 or the 2nd the 1st; Owing to handle with flowing of the vertical direction of face lasting with respect to this; Therefore, can be to handling processing the flowing that is produced with the face rotation with the streamlined additional vertical direction that flows of the spirrillum between face.This processing can be embodied as 1 ℃～400 ℃ with the temperature head between face, is preferably 5 ℃～100 ℃.

And the turning axle 50 of this device is not defined as vertically and disposes.For example, also can be configuration obliquely.In processing,, can get rid of the influence of gravity in fact through at the fluidic film of two processing with face 1, formation between 2.Shown in figure 25, the 1st d1 of importing portion is consistent with the axle center of the 2nd annulus 20 in the 2nd carriage 21, and vertically extends up and down.But; The 1st d1 of importing portion is not limited to consistent with the axle center of the 2nd annulus 20; Be processed liquid as long as can supply with the 1st, in the middle body 22 of the 2nd carriage 21, also can be arranged on the position beyond the above-mentioned axle center to two annulus, 10,20 enclosed spaces; And, also can be non-vertical but oblique extension.Which no matter under the situation of arrangement angles,, can produce with respect to handle with face vertical mobile through handling with the thermograde between face.

Above-mentioned processing is with in the fluidic thermograde between face, if this thermograde is little, then only convection cell carries out thermal conduction, and still, thermograde is in case above certain threshold value, can produce so-called shellfish Nader to flow phenomenon in the fluid.This phenomenon; Handle between use face distance for L, universal gravity constant for g, fluidic volume thermal expansion rate for β, fluidic dynamic viscosity coefficient for ν, fluidic thermometric conductivity for α, when handling temperature head between use face for Δ T, arranged by Rayleigh (レ イ リ one) number Ra with the no non-dimensional number of following formula definition.

Ra＝L ³·g·β·ΔT/(α·ν)

The critical Rayleigh number that begins to produce the Bei Nade convection current is different with the interfacial character of object being treated fluidic with face according to handling, but is approximately 1700.Produce the Bei Nade convection current during greater than this threshold value.And, when this Rayleigh number Ra satisfies greater than 10 ¹⁰Near the condition of value the time, fluid is a turbulent state.Promptly; Through regulating this processing with the temperature head Δ T between face or handle distance L with face; And regulate this device so that Rayleigh number Ra is a mode more than 1700, can between handling, produce with respect to handle mobile with the vertical direction of face, can implement above-mentioned operation with face.

But the processing of above-mentioned shellfish Nader convection current about 1～10 μ m is not easy in the distance between face to produce.Tight, above-mentioned Rayleigh number is applicable to the fluid in the interval below the 10 μ m, and when studying the occurrence condition of Bei Nade convection current, if be water, then its temperature head is necessary for more than thousands of ℃, is difficult in the reality realize.Shellfish Nader convection current is by the formed convection current of the density difference of fluidic thermograde, promptly relevant with gravity convection current.The possibility that between the processing use face below the 10 μ m is the microgravity field is high, and in such situation, the buoyancy convection current is suppressed.That is the situation that, in this device, produces the Bei Nade convection current realistically is to handle with the situation of the distance between face above 10 μ m.

When the distance between the use face of processing is 1～10 μ m left and right sides, is not to produce convection current, but produces convection current through the fluidic surface tension difference that thermograde produced through density difference.Such convection current is kalimeris brother Buddhist nun convection current; Handle between use face distance for L, fluidic dynamic viscosity coefficient for ν, fluidic thermometric conductivity for α, the temperature head handled between use face are ρ, capillary temperature factor (capillary thermograde) when be σ for Δ T, fluidic density, counted Ma by the kalimeris brother Buddhist nun of the non-dimensional number that defines with following formula and arrange.

Ma＝σ·ΔT·L/(ρ·ν·α)

The critical kalimeris brother Buddhist nun number that begins to produce kalimeris brother Buddhist nun convection current is about 80, under greater than the condition of this value, produces kalimeris brother Buddhist nun convection current.Promptly; Through regulate the temperature head Δ T between this processing use face or handle use face distance L, to regulate this device so that kalimeris brother Buddhist nun counts Ma be more than 80; Even the small stream below the 10 μ m also can produce flowing of vertical direction with respect to handling with face between handling with face, can implement above-mentioned operation.

Formula below the calculating of Rayleigh number is used.

[numerical expression 1]

$\mathrm{Ra}=\frac{{\mathrm{<figure-callout\; id="3"\; label="L"\; filenames="HDA0000103002870000091.png,HDA0000103002870000101.png"\; state="\{\{state\}\}">L</figure-callout>}}^3\&CenterDot;\mathrm{\&beta;}\&CenterDot;g}{v\&CenterDot;\mathrm{\&alpha;}}\mathrm{\&Delta;T}$

ΔT＝(T ₁-T ₀)

$\mathrm{\&alpha;}=\frac{k}{\mathrm{\&rho;}\&CenterDot;C_p}$

L: handle with the distance between face [m] β: volume thermal expansion rate [1/K], g: universal gravity constant [m/s ²]

ν: dynamic viscosity coefficient [m ²/ s], α: thermometric conductivity [(m ²/ s)], Δ T: handle with the temperature head between face [K]

ρ: density [kg/m ³], Cp: specific heat at constant pressure [J/kgK], k: thermal conductivity [W/mK]

T ₁: handle temperature [K], T with the high temperature side of face ₀: handle temperature [K] with the low temperature side of face

Rayleigh number in the time will beginning to produce the Bei Nade convection current is as critical Rayleigh number Ra _cSituation under, this moment temperature head Δ T _C1Can try to achieve as follows.

[numerical expression 2]

$\mathrm{\&Delta;}{\mathrm{<figure-callout\; id="1"\; label="T\; C"\; filenames="HDA0000103002870000021.png,HDA0000103002870000041.png"\; state="\{\{state\}\}">T</figure-callout>}}_C=\frac{{\mathrm{Ra}}_C\&CenterDot;v\&CenterDot;\mathrm{\&alpha;}}{{\mathrm{<figure-callout\; id="3"\; label="L"\; filenames="HDA0000103002870000091.png,HDA0000103002870000101.png"\; state="\{\{state\}\}">L</figure-callout>}}^3\&CenterDot;\mathrm{\&beta;}\&CenterDot;g}$

Kalimeris brother Buddhist nun counts the calculating of Ra and uses following formula.

[numerical expression 3]

$\mathrm{Ma}=\frac{{\mathrm{\&sigma;}}_t\&CenterDot;L}{\mathrm{\&rho;}\&CenterDot;v\&CenterDot;\mathrm{\&alpha;}}\mathrm{\&Delta;T}$

ΔT＝(T ₁-T ₀)

$\mathrm{\&alpha;}=\frac{k}{\mathrm{\&rho;}\&CenterDot;C_p}$

L: handle with the distance between face [m] ν: dynamic viscosity coefficient [m ^2/S], α: thermometric conductivity [(m ²/ s)]

Δ T: handle with the temperature head between face [K] ρ: density [kg/m ³], Cp: specific heat at constant pressure [J/kgK]

K: thermal conductivity [W/mK], σ _t: surface tension temperature factor [N/mK]

T ₁: handle temperature [K], T with the high temperature side of face ₀: handle temperature [K] with the low temperature side of face

Count Ma as critical kalimeris brother Buddhist nun falling the kalimeris brother Buddhist nun number that begins to produce kalimeris brother Buddhist nun convection current _cSituation under, this moment temperature head Δ T _C2Can try to achieve as follows.

[numerical expression 4]

$\mathrm{\&Delta;}{\mathrm{<figure-callout\; id="2"\; label="T\; C"\; filenames="HDA0000103002870000021.png,HDA0000103002870000031.png"\; state="\{\{state\}\}">T</figure-callout>}}_C=\frac{{\mathrm{Ma}}_C\&CenterDot;\mathrm{\&rho;}\&CenterDot;v\&CenterDot;\mathrm{\&alpha;}}{{\mathrm{\&sigma;}}_t\&CenterDot;L}$

Below, further particularly for the reaction that generates nanoparticle, according to below various embodiment specify the present invention.But the present invention is not limited to following instance.

(A) pigment nanoparticle

Below, to using the forced ultra-thin film rotating reaction method, the reaction that generates pigment nanoparticle shown in figure 30 is described.

(sour paste method (acid pasting method))

In acid paste method, use under the situation of forced ultra-thin film rotating reaction method; At first; From the 1st d1 of importing portion as 1 stream; Will as the 1st fluidic water or basic soln import can near discretely each other the subtend configuration, at least one side with respect to the processing of the opposing party's rotation with 1,2 in face, the film fluid that formation is made up of the 1st fluid between this processing is with face.

Then, from the 2nd d2 of importing portion, will contain as the 2nd fluidic and be dissolved with the fluid that reactant is the acid of pigment material (pigment acidic solution) and directly import the above-mentioned film fluid that constitutes by the 1st fluid as other stream.

As stated; Can supply with to press and be applied to through fluidic the processing that is rotated with the pressure equilibrium of the pressure between the face with fixed distance processing with face 1, between 2, when carrying out that the 1st fluid and the 2nd fluid kept the ultrathin membrane state, moment the reaction of mixed, generation pigment particles.

What explain is, owing to can carry out above-mentioned reaction with face 1, between 2 and get final product handling, therefore, also can import the 2nd fluid through the 1st d1 of importing portion on the contrary with above-mentioned, imports the 1st fluid through the 2nd d2 of importing portion.That is, the appellation of the what is called the 1st, the 2nd in each solvent is the n of the solvent of a plurality of existence of expression, and just also can there be the solvent more than the 3rd in the mark in order to discern.

The 1st fluid as stated, for water or contain the solution of basic soln.Water is preferably ion exchanged water, pure water, or steam the water stay water etc. to make with extra care.In addition, as basic soln, the ammoniacal liquor of can giving an example, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution etc.

As being used for the 2nd fluidic strong acid, if demonstration is just no problem to the solvability of pigment, not to its special qualification, for example under the situation of acidic aqueous solution; Can use sulfuric acid, hydrochloric acid, nitric acid, trifluoroacetic acid; But, can preferably use strong acid, the particularly vitriol oil more than 95%.

And, in the 1st fluid or the 2nd fluid, for the purpose of the control of pigment crystal type or the quality control of pigment etc., also can mixed organic solvents.Can use known organic solvent as organic solvent.In addition, except that organic solvent, also can contain segmented copolymer or high molecular polymer, the dispersion agent of tensio-active agent etc.

(reprecipitation method)

Secondly; In reprecipitation method, use under the situation of forced ultra-thin film rotating reaction method; At first, from the 1st d1 of importing portion as 1 stream, will as the 1st fluidic, for pigment be poor solvent, with after state the compatible solvent of solvent; Importing can near discretely each other subtend set, at least one side with respect to the processing of the opposing party's rotation with 1,2 in face, the film fluid that constitutes by the 1st fluid with 1,2 formation of face in this processing.

Then,, will contain the fluid of the organic solvent that is dissolved with pigment material, directly import the above-mentioned film fluid that constitutes by the 1st fluid as the 2nd fluidic from the 2nd d2 of importing portion as other stream.

As stated; Can supply with to press and be applied to through fluidic the processing that is rotated with face 1, between 2 pressure pressure equilibrium and with fixed distance processing with face 1, between 2, when carrying out that the 1st fluid and the 2nd fluid kept the ultrathin membrane state, moment the reaction of mixed, generation pigment particles.

What explain is, owing to can carry out above-mentioned reaction with face 1, between 2 and get final product handling, therefore, also can import the 2nd fluid through the 1st d1 of importing portion on the contrary with above-mentioned, imports the 1st fluid through the 2nd d2 of importing portion.That is, the appellation of the what is called the 1st, the 2nd in each solvent is the n of the solvent of a plurality of existence of expression, and just also can there be the solvent more than the 3rd in the mark in order to discern.

As the 1st fluid as stated, as long as be poor solvent, form the consistency of the solvent of the 2nd fluidic pigment, or not still, be not preferably selected from water to its special qualification with dissolving for pigment; Alcohol is solvent, and ketone is solvent, and ether is solvent, fragrant family solvent; Dithiocarbonic anhydride, fatty family solvent, nitrile is a solvent, sulfoxide is a solvent; Halogen is solvent, and ester is a solvent, ionic solution, or the mixed solvent more than 2 kinds wherein.

As being used for the 2nd fluidic organic solvent,,, still, can preferably use 1-Methyl-2-Pyrrolidone not to its special qualification as long as demonstration is just no problem to the solvability of pigment; 1,3-dimethyl--2-imidazolidone, 2-Pyrrolidone, ε-hexyl propionamide, methane amide; The N-NMF, N, dinethylformamide, ethanamide, N-methylacetamide; DMAC N,N, N-methyl propanamide, HMPA.

And, in the 1st fluid or the 2nd fluid, also can contain segmented copolymer, high molecular polymer, the dispersion agent of tensio-active agent etc.

(pH adjusts method)

Then; In pH adjustment method, use under the situation of forced ultra-thin film rotating reaction method; At first; From the 1st d1 of importing portion, the pigment that pH is changed separated out with solution import the above-mentioned processing that is rotated with 1,2 in face as the 1st fluid, the film fluid that formation is made up of the 1st fluid between this processing is with face as 1 stream.

Then; From the 2nd d2 of importing portion as other stream; To in any of the mixing solutions of acid or alkaline pH adjustment solution or above-mentioned pH adjustment solution and organic solvent, dissolve the pigment solution of at least a kind of pigment as the 2nd fluidic, directly import the above-mentioned film fluid that constitutes by the 1st fluid.

As stated; Can supply with press and be applied to the processing that is rotated through fluidic with face 1; The pressure equilibrium of the pressure between 2 and with fixed distance processing with face 1, between 2, when carrying out that the 1st fluid and the 2nd fluid kept the ultrathin membrane state, mixed, the reaction that generates pigment particles in moment ground.

Particularly; For example; With in certain organic solvent hardly the dissolved pigment dyestuff be added in the solution of the alkalescence of in above-mentioned organic solvent, having added alkaline matter; Make its dissolving thus and form organic pigment solution (the 2nd fluid); The pigment of solvent that this pigment dyestuff solution is added to the organic solvent that makes water or other organic solvent or above-mentioned alkali-free property material or contains acid is separated out with in the solution (the 1st fluid), and the pH of pigment dyestuff solution changes, and can carry out the reaction that pigment is separated out with face 1, between 2 in processing.Under this situation, the bronsted lowry acids and bases bronsted lowry that is added can be selected to add in order to dissolve pigment, or add for it is separated out according to the kind of pigment.

What explain is, owing to can carry out above-mentioned reaction with face 1, between 2 and get final product handling, therefore, also can import the 2nd fluid through the 1st d1 of importing portion on the contrary with above-mentioned, imports the 1st fluid through the 2nd d2 of importing portion.That is, the appellation of the what is called the 1st, the 2nd in each fluid is that the fluidic n of a plurality of existence of expression is individual, and just also can there be the fluid more than the 3rd in the mark in order to discern.

Separate out as the 1st fluidic pigment and to use solution; As stated; As long as the solution that changes for the pH that can make above-mentioned pigment solution, be not show solvability, perhaps in the pigment of purpose to separate out, it is little the getting final product of being contained in the 2nd fluidic pigment solution of solvent that the solvability of pigment is likened to, it is not done special qualification; Can be water or organic solvent, or their mixture constitutes.Be preferably ion exchanged water, pure water or steam the water that the quilt that stays water etc. has been made with extra care as water.As organic solvent, not special the qualification, can enumerate methyl alcohol, ethanol, Virahol, the trimethyl carbinol is the unary alcohol solvent of representative; Terepthaloyl moietie, Ucar 35, glycol ether, polyoxyethylene glycol, thiodiglycol, two thiodiglycols, 2-methyl isophthalic acid, 3-propane diol, 1,2,6-hexane triol, alkyne diol verivate, glycerine or TriMethylolPropane(TMP) etc. are the polyalcohols solvent of representative; 1-Methyl-2-Pyrrolidone, 1; 3-dimethyl--2-imidazolidone, 2-Pyrrolidone, ε-hexyl propionamide, methane amide, N-NMF, N; Dinethylformamide, ethanamide, N-methylacetamide, N; The amides solvent of N-N,N-DIMETHYLACETAMIDE, N-methyl propanamide, HMPA, urea or tetramethyl-urea etc.; In addition, glycol monomethyl methyl (or ethyl) ether, the rudimentary monoalkyl ethers solvent of the polyvalent alcohol of Diethylene Glycol monomethyl (or ethyl) ether or triethylene glycol monomethyl (or butyl) ether etc.; Multifunctional type of solvent of the sulfur-bearing class solvent of polyethers solvent, tetramethylene sulfone, DMSO 99.8MIN. or the 3-cyclobufene sultone etc. of ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (Diglyme) or triethylene glycol dimethyl ether (Triglyme) etc., diacetone alcohol, diethylolamine etc.; The carboxylic-acid solvent of acetate, toxilic acid, docosahexenoic acid, trichoroacetic acid(TCA) or trifluoroacetic acid etc.; The sulfonic acid class solvent of methanesulfonic or trifluoromethayl sulfonic acid etc.; The benzene series solvent of benzene,toluene,xylene etc.

And pH adjustment material, the formation that also can in solvent, add as acid or alkali are implemented as acid or alkaline pH adjustment solution.PH adjustment material under this situation is not done special qualification, under the situation of alkali, is Lithium Hydroxide MonoHydrate; Sodium hydroxide, Pottasium Hydroxide, calcium hydroxide; Or the mineral alkali or the trialkylamine of hydrated barta etc., two azo dicyclo undecylenes, the organic bases of metal alcoholate etc.Under the situation of acid, be the mineral acid of formic acid, nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid etc., or acetate, trifluoroacetic acid, oxalic acid, methanesulfonic, or the organic acid of trifluoromethayl sulfonic acid etc.These pH adjustment materials can add, also can form the aqueous solution or organic solvent solution with solid state and add and implement.

The solvent that in as the 2nd fluidic pigment solution, uses also can use the solvent identical with the 1st fluid.But, preferably select pigment ground solvability than the big solvent of solvent that is contained in the 1st fluid.And, also can add the material identical as pH adjustment material and implement with the 1st fluid.The preferred pH adjustment material of selecting is so that the 2nd fluid is bigger than the solvent that is contained in the 1st fluid for the solvability of pigment.

And, the mixing solutions (pH adjust solution) of contained solvent and pH adjustment material in above-mentioned the 1st fluid and the 2nd fluid, the solution state use that can dissolve each other fully with all materials also can be used with suspended state.

And, in the 1st fluid or the 2nd fluid, for the purpose of the control of pigment crystal type or the quality control of pigment etc., also can mixed organic solvents.Can use known organic solvent as organic solvent.In addition, except that organic solvent, also can contain the dispersion agent of high molecular polymer, segmented copolymer etc., tensio-active agent.

As the pigment that uses in each above-mentioned method, do not do special restriction, still, can enumerate many ring quinone pigments, perylene series pigments, azo pigment, indigo pigment, quinacridone pigment, the known pigment dyestuff of phthalocyanine pigment etc.

In addition, comprise granular solids, the such pigment of dye composition as pigment.As the instance of pigment, inorganic Achromatic color pigment is arranged, organic and inorganic Chromatic color pigment in addition, also can use the pigment of colourless or light color, metalluster pigment etc.For the present invention, also can use novel synthetic pigment.Below enumerate the specific examples of pigment.

As the pigment of black, for example, can enumerate following material.That is, Raven1060, Raven1080, Raven 1170; Raven 1200, and Raven 1250, and Raven 1255, and Raven 1500; Raven 2000, and Raven 3500, and Raven 5250, and Raven 5750; Raven 7000, Raven 5000 ULTRAII, Raven 1190 ULTRAII (above, Columbia Carbon society system).In addition, Black PearlsL, Mogul-L, Regal 400R, Regal 660R, Regal 330R, Monarch 800, and Monarch 880, and Monarch 900, and Monarch 1000, and Monarch 1300, Monarch 1400 (above, cabot society system).In addition, Color BlackFW1, Color Black FW2, Color Black FW200; Color Black 18, Color Black S160, Color Black S170, Special Black 4; Special Black4A, Special Black 6, Printex 35, Printex U; Printex 140U, Printex V, Printex 140V (above, Degussa society system).In addition, No.25, No.33, No.40, No.47, No.52, No.900, No.2300, MCF-88, MA600, MA7, MA8, MA100 (above, Mitsubishi Chemical society system) etc.But, be not defined as these pigment.

As the pigment of cyan, can enumerate following material.That is, C.I. Pigment blue-1, C.I. Pigment blue-2, C.I. Pigment blue-3.In addition, C.I. Pigment blue-15, C.I. Pigment blue-15:2, C.I. Pigment blue-15:3, C.I. Pigment blue-15:4.In addition, C.I. Pigment blue-16, C.I. Pigment blue-22, C.I. Pigment blue-60 etc.

As carmine pigment, can enumerate following material.That is, C.I. Pigment red-5, C.I. Pigment red-7, C.I. Pigment red-12.In addition, C.I. Pigment red-48, C.I. Pigment red-48:1, C.I. Pigment red-57, C.I. Pigment red-112.In addition, C.I. Pigment red-122, C.I. Pigment red-123, C.I. Pigment red-146, C.I. Pigment red-168.In addition, C.I. Pigment red-184, C.I. Pigment red-202, C.I. Pigment red-207 etc.

As xanchromatic pigment, can enumerate following material.That is, C.I. Pigment Yellow 73-12, C.I. Pigment Yellow 73-13, C.I. Pigment Yellow 73-14, C.I. Pigment Yellow 73-16.In addition, C.I. Pigment Yellow 73-17, C.I. Pigment Yellow 73-74, C.I. Pigment Yellow 73-83, C.I. Pigment Yellow 73-93.In addition, C.I. Pigment Yellow 73-95, C.I. Pigment Yellow 73-97, C.I. Pigment Yellow 73-98, C.I. Pigment Yellow 73-114.In addition, C.I. Pigment Yellow 73-128, C.I. Pigment Yellow 73-129, C.I. Pigment Yellow 73-151, C.I. Pigment Yellow 73-154 etc.

And, except that above-mentioned black, cyan, carmetta, the xanchromatic pigment, also can use various pigment according to the purpose look.Can enumerate such violet pigment of pigment violet rowland-23 or the such veridian of Pigment green-7 typically, the orange pigments as pigment orange-43; As long as can implement but appear as the color of pigment.

In addition, also can use dyestuff equally among the present invention with pigment.As an example, can enumerate the C.I. solvent blue ,-33 ,-38 ,-42 ,-45 ,-53 ,-65 ,-67 ,-70 ,-104 ,-114 ,-115 ,-135.In addition, C.I. solvent red ,-25 ,-31 ,-86 ,-92 ,-97 ,-118 ,-132 ,-160 ,-186 ,-187 ,-219.In addition, C.I. solvent yellow ,-1 ,-49 ,-62 ,-74 ,-79 ,-82 ,-83 ,-89 ,-90 ,-120 ,-121 ,-151 ,-153 ,-154 etc.

Also can use water-soluble dye.As an example, it is directly black to enumerate C.I., and-17 ,-19 ,-22 ,-32 ,-38 ,-51 ,-62 ,-71 ,-108 ,-146 ,-154; C.I. directly yellow ,-12 ,-24 ,-26 ,-44 ,-86 ,-87 ,-98 ,-100 ,-130 ,-142; C.I. directly red ,-1 ,-4 ,-13 ,-17 ,-23 ,-28 ,-31 ,-62 ,-79 ,-81 ,-83 ,-89 ,-227 ,-240 ,-242 ,-243; C.I. sun blue ,-6 ,-22 ,-25 ,-71 ,-78 ,-86 ,-90 ,-106 ,-199; C.I. direct orange s ,-34 ,-39 ,-44 ,-46 ,-60; C.I. direct VT ,-47 ,-48; C.I. direct brown ,-109; C.I. sun green, the substantive dyestuff of-59 grades, C.I. erie black ,-2 ,-7 ,-24 ,-26 ,-31 ,-52 ,-63 ,-112 ,-118 ,-168 ,-172 ,-208; C.I. turmeric yellow ,-11 ,-17 ,-23 ,-25 ,-29 ,-42 ,-49 ,-61 ,-71; C.I. Xylene Red ,-1 ,-6 ,-8 ,-32 ,-37 ,-51 ,-52 ,-80 ,-85 ,-87 ,-92 ,-94 ,-115 ,-180 ,-254 ,-256 ,-289 ,-315 ,-317; C.I. acid blue ,-9 ,-22 ,-40 ,-59 ,-93 ,-102 ,-104 ,-113 ,-117 ,-120 ,-167 ,-229 ,-234 ,-254; C.I. von Muller's indicator ,-7 ,-19; C.I. acid violet rowland, the matching stain of-49 grades, the C.I. reaction is black, and-1 ,-5 ,-8 ,-13 ,-14 ,-23 ,-31 ,-34 ,-39; C.I. reaction is yellow, and-2 ,-3 ,-13 ,-15 ,-17 ,-18 ,-23 ,-24 ,-37 ,-42 ,-57 ,-58;-64 ,-75 ,-76 ,-77 ,-79 ,-81 ,-84 ,-85 ,-87 ,-88 ,-91 ,-92;-93 ,-95 ,-102 ,-111 ,-115 ,-116 ,-130 ,-131 ,-132 ,-133 ,-135 ,-137;-139 ,-140 ,-142 ,-143 ,-144 ,-145 ,-146 ,-147 ,-148 ,-151 ,-162 ,-163; C.I. react red ,-3 ,-13 ,-16 ,-21 ,-22 ,-23 ,-24 ,-29 ,-31 ,-33 ,-35 ,-45;-49 ,-55 ,-63 ,-85 ,-106 ,-109 ,-111 ,-112 ,-113 ,-114 ,-118 ,-126 ,-128;-130 ,-131 ,-141 ,-151 ,-170 ,-171 ,-174 ,-176 ,-177 ,-183 ,-184 ,-186 ,-187;-188 ,-190 ,-193 ,-194 ,-195 ,-196 ,-200 ,-201 ,-202 ,-204 ,-206 ,-218 ,-221; C.I. reaction is blue, and-2 ,-3 ,-5 ,-8 ,-10 ,-13 ,-14 ,-15 ,-18 ,-19 ,-21 ,-25 ,-27 ,-28;-38 ,-39 ,-40 ,-41 ,-49 ,-52 ,-63 ,-71 ,-72 ,-74 ,-75 ,-77 ,-78 ,-79 ,-89;-100 ,-101 ,-104 ,-105 ,-119 ,-122 ,-147 ,-158 ,-160 ,-162 ,-166 ,-169 ,-170 ,-171 ,-172;-173 ,-174 ,-176 ,-179 ,-184 ,-190 ,-191 ,-194 ,-195 ,-198 ,-204 ,-211 ,-216 ,-217; C.I. reaction is orange, and-5 ,-7 ,-11 ,-12 ,-13 ,-15 ,-16 ,-35 ,-45 ,-46 ,-56 ,-62 ,-70 ,-72 ,-74 ,-82 ,-84 ,-87 ,-91 ,-92 ,-93 ,-95 ,-97 ,-99; C.I. reaction is purple, and-1 ,-4 ,-5 ,-6 ,-22 ,-24 ,-33 ,-36 ,-38; C.I. react green ,-5 ,-8 ,-12 ,-15 ,-19 ,-23; C.I. reaction is brown, and-2 ,-7 ,-8 ,-9 ,-11 ,-16 ,-17 ,-18 ,-21 ,-24 ,-26 ,-31, the reactive dye of-32 ,-33 grades; C.I. basic black ,-2; C.I. alkaline red ,-1 ,-2 ,-9 ,-12 ,-13 ,-14 ,-27; C.I. reflex blue ,-1 ,-3 ,-5 ,-7 ,-9 ,-24 ,-25 ,-26 ,-28 ,-29; C.I. alkaline VT ,-7 ,-14 ,-27; C.I. food is black, and-1 ,-2 etc.

Employable dyestuff can be known dyestuff, also can be novel dyestuff.For example, can use the such substantive dyestuff of the following stated, matching stain, basic dyestuff, chemically-reactive dyes, food be with the water-soluble dye of pigment, fat-soluble (oil soluble) dyestuff perhaps, the insoluble pigment of dispersed dye.These dyestuffs also can be with solidification the state use.Aspect this preferably, for example can use oil-soluble colourant.

Oil-soluble colourant described in the present invention are meant the dyestuff that is dissolved in the organic solvent, are also referred to as lipid-soluble dye.

As tensio-active agent and dispersion agent, can use the various commercially available article that in the dispersing of pigments purposes, use.It is not done special restriction, for example, can use the such Witco 1298 Soft Acid system of Neogen R-K (the first industrial pharmacy), Solsperse 20000, and Solsperse 24000, and Solsperse 26000; Solsperse 27000, and Solsperse 28000, Solsperse41090 (above, Avecia society system), and Disperbyk 160, and Disperbyk 161, Disperbyk162; Disperbyk 163, and Disperbyk 166, and Disperbyk 170, and Disperbyk 180, and Disperbyk 181, and Disperbyk 182; Disperbyk 183, and Disperbyk 184, and Disperbyk 190, and Disperbyk 191, and Disperbyk 192, and Disperbyk 2000; Disperbyk 2001 (above, BYK-Chemie society system), Polymer 100, and Polymer 120, and Polymer 150, and Polymer 400, and Polymer 401; Polymer 402, and Polymer 403, and Polymer 450, and Polymer 451, and Polymer 452; Polymer 453, EFKA-46, EFKA-47, EFKA-48, EFKA-49; EFKA-1501, EFKA-1502, EFKA-4540, EFKA-4550 (above, EFKA Chemical society system), FLOWNON DOPA-158; FLOWNON DOPA-22, FLOWNON DOPA-17, FLOWNON G-700, FLOWNON TG-720W, FLOWNON-730W; FLOWNON-740W, FLOWNON-745W (chemistry society of above, common prosperity society system), AJISPER PA 111, AJISPER PB 711, AJISPER PB 811; AJISPER PB 821, AJISPER PW 911 (above, aginomoto society system), JONCRYL 678, JONCRYL679, JONCRYL 62 (above, JHONSON POLYMER society system) etc.These tensio-active agents and dispersion agent can use separately, also can more than 2 kinds and use.

In the present invention as segmented copolymer, can enumerate as follows as an example in addition.That is, acrylic acid series, methylacrylic acid based block copolymer, the segmented copolymer of PS and other addition polymerization system or polycondensation system has the segmented copolymer of the block of polyoxyethylene, polyoxy alkylidene.And, also can use known in the past segmented copolymer.Used segmented copolymer is preferably amphipathic among the present invention.As concrete preferred form, can enumerate comprise hydrophobic segment and organic acid or the unitary hydrophilic segment of its ion salt Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock.In addition, the preferred use has hydrophobic segment and has organic acid or have the triblock copolymer of unitary hydrophilic segment of its ion salt and other block.Under the situation of triblock copolymer, preferably use as hydrophobic segment, the hydrophilic segment of nonionic has the form of organic acid or the unitary hydrophilic segment of its ion salt, and the meaning aspect of the stabilization of interior bag state also is preferred.For example,, use pigment material and modulate dispersion liquid, can make in the micella that wraps in triblock copolymer formation in the pigment, also can so form the ink composite of bag type in the pigment as the water of solvent if use above-mentioned triblock copolymer.In addition, also can make this dispersive composition particle particle diameter very consistent evenly.And then also can make its dispersion state very stable.Handle if use the forced ultra-thin film rotating reaction method to carry out these, the very inhibition homogeneity of the particle diameter of pigment nanoparticle also further improves.

In addition except that above-mentioned each the method, as the pigment nanoparticle method of manufacture of having used the forced ultra-thin film rotating reaction method, also can be in this film fluid direct synthetic dyestuff.As an instance; Under the situation of the synthetic example of copper phthalocyanine, also can with through with phthalandione or derivatives thereof, copper or its compound, urea or derivatives thereof and catalyzer in organic solvent or its method of obtaining copper phthalocyanine of reacting in the presence of not be representative, use the direct synthetic dyestuff of various reactions.Thus; Though need be in method till now to the operation of pulverizing because of the thick pigment particles that synthesis procedure produced; But this becomes and there is no need; Even and then needing under the situation of pulverizing process, also can in the film fluid, give shearing force according to operating condition, contain pulverizing process.

Among the present invention, mix the mixing in the stream, can under the laminar flow domination, carry out, also can under the turbulent flow domination, carry out.

And, can be with handling with heating between face, cooling, or to processing with irradiating microwaves between face.In addition also can be to handling with irradiation ultraviolet radiation between face (UV), or in addition to processing with giving ultrasonic energy between face.Particularly, be provided with under the situation of temperature head with face 2 with face 1 and the 2nd processing,, have the advantage that promotes reaction thus owing to can in the film fluid, convection current take place in the 1st processing.

More specifically, for heating, cooling for example can be heated, cool off the film fluid through reason throughout with well heater or the big envelope through thermal medium, cold medium are set at least one side of portion 10,20 or two sides.Perhaps, carry out the heating of treat fluid, the promotion of reaction through reason throughout with the microwave generating apparatus such as magnetron that are provided for irradiating microwaves at least one side of portion 10,20 or two sides.In addition, for irradiation ultraviolet radiation (UV), for example can face film fluid irradiation ultraviolet radiation (UV) from corresponding processing usefulness through the element of reason throughout with the uv lamp that irradiation ultraviolet radiation is set at least one side of portion 10,20 or two sides etc.In addition, for giving ultrasonic energy, for example can also can in the container of UW atmosphere, handle and implement with at least one side of portion 10,20 or two sides ultrasonic oscillator being set through reason throughout with the hybrid reaction between face.

In addition; Through can guarantee to reduce pressure or the container of vacuum state in carry out above-mentioned separate out, make handle 2 sides that the back fluid is discharged from least and form decompression or vacuum state; The degassing of contained gas in gas that carries out taking place in the evolution reaction and the above-mentioned fluid, or above-mentioned fluidic desolventizing.Thus, even when the pigment nanoparticle is separated out, carry out containing the fluid of handling with the pigment nanoparticle of separating out between face under the situation of desolventizing processing, discharge with atomize with face from handling, its fluidic surface-area increases, and desolventizing efficient is very high.Therefore than till now also simply, 1 operation is carried out the manufacturing processing and the desolventizing processing of pigment nanoparticle in fact.

In addition; As stated, except that the 1st d1 of importing portion, the 2nd d2 of importing portion, the 3rd d3 of importing portion can be set on treatment unit also; In this case; In the for example above-mentioned acid paste method, can from each importing portion with water or basic soln, contain the fluid of the acid that is dissolved with pigment, for organic solvent of the purpose of the control of pigment crystal type or the quality control of pigment etc. etc. imports treatment unit respectively.In addition, under the situation that adopts the pH adjustment, can separate out with solution, contain the fluid of pigment solution, for the organic solvent of purposes such as the control of pigment crystal type or quality control etc. imports treatment unit respectively from the pigment that each importing portion will make pH change.Like this, can each manage the concentration and the pressure of each solution, can more critically control the reaction that the pigment nanoparticle generates.Even under the situation that is provided with the importing portion more than the 4th, the fluid sectionalization that equally also can be so will import to treatment unit.

Forced ultra-thin film rotating reaction method in the application's invention; Change because the Reynolds (レ イ ノ Le ズ) of its small stream is counted, therefore can make single dispersion, the good pigment nanoparticle of redispersibility according to purposes such as particle diameter, particle shape, crystal types.And, through its oneself's discharge property,, there is not the obstruction of product even under situation with evolution reaction yet, do not need big pressure.So, can stably make the pigment nanoparticle, in addition, excellent in safety does not almost have sneaking into of impurity, and detergency is also good.And, because can amplify, therefore the method for manufacture of the also high pigment nanoparticle of its productivity can be provided according to the turnout of purpose

Below, enumerate relevant pigment nanoparticle embodiment and explain that in further detail still, the present invention is not limited to these embodiment.

What explain is; In following embodiment; So-called " from central authorities "; Refer to such an extent that be the meaning of " from the 1st d1 of importing portion " of treatment unit shown in above-mentioned, Fig. 1 (A), the 1st fluid is meant that the above-mentioned the 1st is processed liquid, that the 2nd fluid is meant is above-mentioned, treatment unit shown in Fig. 1 (A) " that import from the 2nd d2 of importing portion, above-mentioned the 2nd is processed liquid.

Shown in Fig. 1 (A), can be used as in the device of forced ultra-thin film rotating reaction method; In can be near isolating mutual subtend sets, at least one side is rotated with respect to the opposing party processing film fluid with face 1, formation between 2; The reaction unit that mixes equably; To contain the pasty liquid that in the vitriol oil, is dissolved with copper phthalocyanine and the aqueous solution of dispersion agent and in the film fluid, collaborate, and mix equably, simultaneously the pigment nanoparticle separated out.

(embodiment A 1)

On one side will be as the 1st fluidic Disper BYK 184 (the BYK Chemie society system) aqueous solution from central authorities; Carry out liquor charging for 20 ℃ with supply pressure/back pressure=0.02MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature, will as 2nd fluidic 3% copper phthalocyanine/98% concentrated sulfuric acid aqueous solution with 10ml/min import to processing with face 1,2 between on one side.The pigment nanoparticle dispersion liquid is discharged from face from handling.Particle size distribution device (day machine dress society system of laser Doppler method has been used in use; Trade(brand)name microtrac UPA150) size-grade distribution of the pigment nanoparticle dispersion liquid that obtains is measured; The result is 14nm for volume average particle size, and the CV value of its size-grade distribution is 13%.In addition, with dialysis tubing with pure water with the dialysis of this pigment nanoparticle dispersion liquid after 24 hours, drying obtains pigment nanoparticle powder.Again this powder is put in the ion exchanged water; With high-speed stirring type dispersion machine (trade(brand)name: ClearMix; M technology society system) stir, the result obtains the pigment nanoparticle dispersion liquid once more; Volume average particle size with just obtained with the forced ultra-thin film rotating reaction method identical, volume average particle size is 14nm.

(embodiment A 2)

On one side will be as the 1st fluidic Disper BYK 184 (the BYK Chemie society system) aqueous solution from central authorities; Carry out liquor charging for 20 ℃ with supply pressure/back pressure=0.02MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature, will as 2nd fluidic 3% quinacridone pigment/98% concentrated sulfuric acid aqueous solution with 10ml/min import to processing with face 1,2 between on one side.The pigment nanoparticle dispersion liquid is discharged from face from handling.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains; The result does; Volume average particle size is 15nm, and the CV value of its size-grade distribution is 14%.In addition, with dialysis tubing with this pigment nanoparticle dispersion liquid with pure water dialysis 24 hours after, drying obtains pigment nanoparticle powder.Again this powder is dropped in the ion exchanged water; With high-speed stirring type dispersion machine (trade(brand)name: ClearMix; M technology society system) stir, the result obtains the pigment nanoparticle dispersion liquid once more; Volume average particle size with just obtained with the forced ultra-thin film rotating reaction method identical, volume average particle size is 15nm.

(Comparative examples A 1)

On one side Disper BYK 184 (BYK Chemie society system) aqueous solution 20g is stirred with 20 ℃ of solution temperatures, rotating speed 300rpm in beaker, Yi Bian drop into 3% copper phthalocyanine/98% concentrated sulfuric acid aqueous solution 20g.Obtain the copper phthalocyanine dispersion-s of water system.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and the result is that volume average particle size is 1345nm.In addition, after with dialysis tubing this pigment nanoparticle dispersion liquid being dialysed 24 hours in pure water, drying obtains pigment nanoparticle powder.Again this powder is dropped in the ion exchanged water; With high-speed stirring type dispersion machine (trade(brand)name: ClearMix; M technology society system) stir, the result obtains the pigment nanoparticle dispersion liquid once more; Volume average particle size is also bigger than the volume average particle size that in beaker, obtains, and volume average particle size is 2882nm.

(Comparative examples A 2)

On one side Disper BYK 184 (BYK Chemie society system) aqueous solution 20g is stirred with 20 ℃ of solution temperatures, 300rpm in beaker, Yi Bian drop into 3% quinacridone pigment/98% concentrated sulfuric acid aqueous solution 20g.Obtain the quinacridone pigment dispersion liquid of water system.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment particles dispersion liquid that obtains, and result, volume average particle size are 1833nm.In addition, after with dialysis tubing this pigment nanoparticle dispersion liquid being dialysed 24 hours, carry out drying in pure water, obtain pigment nanoparticle powder.Again this powder is dropped in the ion exchanged water; Stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more; Volume average particle size is bigger than what in beaker, obtain, and volume average particle size is 3345nm.

(embodiment A 3)

On one side will be as the 1st fluidic ion exchanged water from central authorities; Carry out liquor charging for 25 ℃ with supply pressure/back pressure=0.01MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature, will as 2nd fluidic 0.5% non-substituted straight chain shape quinacridone pigment/1-Methyl-2-Pyrrolidone (NMP) solution with 10ml/min import to processing with face 1,2 between on one side.The pigment nanoparticle dispersion liquid is discharged from face from handling.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains; The result; Volume average particle size is 18nm, and the CV value of its size-grade distribution is 17%.In addition, after with dialysis tubing this pigment nanoparticle dispersion liquid being dialysed 24 hours, carry out drying in pure water, obtain pigment nanoparticle powder.The quinacridone pigment that the result of powder x-ray diffraction obtains can be thought and is the γ type.Again this powder is dropped in the ion exchanged water; With high-speed stirring type dispersion machine (trade(brand)name: ClearMix; M technology society system) stirs; The result obtains the pigment nanoparticle dispersion liquid once more, volume average particle size with just obtained with the forced ultra-thin film rotating reaction method identical, volume average particle size is 18nm.

(embodiment A 4)

On one side will be as the 1st fluidic methyl alcohol from central authorities; Carry out liquor charging for 25 ℃ with supply pressure/back pressure=0.01MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature, will as 2nd fluidic 0.5% non-substituted straight chain shape quinacridone pigment/1-Methyl-2-Pyrrolidone (NMP) solution with 10ml/min import to processing with face 1,2 between on one side.The pigment nanoparticle dispersion liquid is discharged from face from handling.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains; The result; Volume average particle size is 20nm, and the CV value of its size-grade distribution is 17%.In addition, after with dialysis tubing this pigment nanoparticle dispersion liquid being dialysed 24 hours, carry out drying in pure water, obtain pigment nanoparticle powder.The quinacridone pigment that the result of powder x-ray diffraction obtains can be thought and is the α type.Again this powder is dropped in the ion exchanged water; With high-speed stirring type dispersion machine (trade(brand)name: ClearMix; M technology society system) stirs; The result obtains the pigment nanoparticle dispersion liquid once more, volume average particle size with just obtained with the forced ultra-thin film rotating reaction method identical, volume average particle size is 20nm.

(Comparative examples A 3)

On one side ion exchanged water 20g is stirred with 25 ℃ of solution temperatures, 300rpm in beaker, Yi Bian drop into 0.5% non-substituted straight chain shape quinacridone pigment/1-Methyl-2-Pyrrolidone (NMP) solution 20g.Obtain the quinacridone pigment dispersion liquid of water system.The particle size distribution device (the trade(brand)name microtracUPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment particles dispersion liquid that obtains, and result, volume average particle size are 2243nm.In addition, after with dialysis tubing this pigment nanoparticle dispersion liquid being dialysed 24 hours, carry out drying in pure water, obtain pigment nanoparticle powder.Again this powder is dropped in the ion exchanged water; Stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more; Volume average particle size is bigger than what in beaker, obtain, and volume average particle size is 2882nm.

(Comparative examples A 4)

On one side with methyl alcohol 20g in beaker with 25 ℃ of solution temperatures, 300rpm stirs, Yi Bian drop into 0.5% non-substituted straight chain shape quinacridone pigment/1-Methyl-2-Pyrrolidone (NMP) solution 20g.Obtain the dispersible pigment dispersion of organic solvent system.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment particles dispersion liquid that obtains, and result, volume average particle size are 3321nm.In addition, after with dialysis tubing this pigment nanoparticle dispersion liquid being dialysed 24 hours, carry out drying in pure water, obtain pigment nanoparticle powder.Again this powder is dropped in the methyl alcohol; Stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more; Volume average particle size is bigger than what in beaker, obtain, and volume average particle size is 4211nm.

The above results is shown in table 1.What explain is that embodiment 1～4 in the table and comparative example 1～4 are represented the foregoing description A1～A4 and Comparative examples A 1～A4 respectively.

The pigment nanoparticle that use obtains in embodiment A 1 cooperates the modulation ink for inkjet shown in following.

The pigment that obtains in the embodiment A 1: 5%

Low dispersal agent molecule (the system Disperse-Aid W-28 of Sannopco Limited society): 1%

0.75% skimmer (the chemistry system Aqualen1435 of common prosperity society): 0.75%

Ion exchanged water: 89.25%

Macromolecule dispersing agent (the system Disper BYK of BYK Chemie society 184): 4%

For the storage stability of above-mentioned ink, estimate though quicken the heavy of pigment, even it is for placing 2 years almost also non-settling levels of pigment with centrifugal settling method.Stop up for syringe needle, after a certain amount of literal typewriting,, still can normally typewrite from first literal not adding state held typewriting again after 30 minutes of cap etc.The typewriting quality, the bleeding of visual valuation literal, smudgy etc. is not for there being the clean typewriting of defective.Weathering resistance is equivalent to the climatic test of condition of the solar irradiation in 1 year, and the change in color after the test is in 5%.

As above-mentioned showing, the ink that utilizes the application to invent, because pigment is dispersed to atomic little particulate, so excellent storage stability, syringe needle does not stop up in addition, and excellent as the ink for inkjet weathering resistance yet.

Secondly; In following embodiment; Shown in Fig. 1 (A); Use can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, the reaction unit that mixes equably in the formed film fluid between 2; The solution and the water phase surfactant mixture that contain Pigment red 254 (structure name: diketopyrrolopyrrolecocrystals ((diketopyrrolopyrrole)) below is designated as PR-254) are collaborated, on one side one side uniform mixing is separated out the pigment nanoparticle in the film fluid in the film fluid.

(embodiment A 5)

To carry out liquor charging for 20 ℃ with supply pressure/back pressure=0.02MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature as the 1st fluidic lauryl sodium sulfate aqueous solution from central authorities on one side, will as the mix suspending solution of 2nd fluidic 1.71w/w%PR-254/82.32w/w% DMSO 99.8MIN. (DMSO)/15.97w/w%8N potassium hydroxide aqueous solution with 1ml/min import processing with face 1,2 between on one side.The pigment nanoparticle dispersion liquid is discharged from face from handling, and the pH of liquid effluent is 11.6.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains is measured, and result, volume average particle size are 13nm.In addition, this pigment nanoparticle dispersion liquid was dialysed in pure water 24 hours, remove sodium lauryl sulphate, behind the DMSO etc., carry out drying, obtain pigment nanoparticle powder with dialysis tubing.Again this powder is dropped in the ion exchanged water; Stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more; Volume average particle size with just obtained with the forced ultra-thin film rotating reaction method identical, be 13nm.

(embodiment A 6)

To carry out liquor charging for 20 ℃ with supply pressure/back pressure=0.02MPa/0.01MPa, rotating speed 500rpm, liquor charging temperature as the 1st fluidic lauryl sodium sulfate aqueous solution from central authorities on one side, will as the mixing solutions of 2nd fluidic 1.71w/w%PR-254/96.70w/w% DMSO 99.8MIN. (DMSO)/1.59w/w%8N potassium hydroxide aqueous solution with 1ml/min import processing with face 1,2 between on one side.The pigment nanoparticle dispersion liquid is discharged from face from handling, and the pH value of liquid effluent is 11.1.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and result, volume average particle size are 12nm.In addition, this pigment nanoparticle dispersion liquid was dialysed in pure water 24 hours, remove sodium lauryl sulphate, behind the DMSO etc., carry out drying, obtain pigment nanoparticle powder with dialysis tubing.Again this powder is dropped in the ion exchanged water; Stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more; Volume average particle size with just obtained with the forced ultra-thin film rotating reaction method identical, be 12nm.

(embodiment A 7)

To carry out liquor charging for 20 ℃ with supply pressure/back pressure=0.05Mpa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature as the 1st fluidic Disperbyk-190 (BYK Chemie society system) propylene glycol methyl ether acetate (PGMEA) solution from central authorities on one side, will as 2nd fluidic 2.55w/w%PR-254/76.55w/w% THF (THF)/0.77w/w% sodium ethylate/20.13w/w% alcoholic acid mixing solutions with 1ml/min import processing with face 1,2 between on one side.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and result, volume average particle size are 17nm.In addition, remove sodium ethylate, behind the THF etc., carry out drying, obtain pigment nanoparticle powder from this pigment nanoparticle dispersion liquid.This powder is dropped among the PGMEA again, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more, and volume average particle size is identical from handling with the face discharge with just, is 17nm.

(Comparative examples A 5)

On one side with lauryl sodium sulfate aqueous solution 100g in beaker with 20 ℃ of solution temperatures; 300rpm stirs, Yi Bian drop into the mix suspending solution 20g of 1.71w/w%PR-254/82.32w/w% DMSO 99.8MIN. (DMSO)/15.97w/w%8N potassium hydroxide aqueous solution.Obtain the pigment nanoparticle dispersion liquid.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and result, volume average particle size are 542nm.In addition, this pigment nanoparticle dispersion liquid was dialysed in pure water 24 hours, remove sodium lauryl sulphate, behind the DMSO etc., carry out drying, obtain pigment nanoparticle powder with dialysis tubing.This powder is dropped in the ion exchanged water again, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more, and volume average particle size is bigger than what in beaker, just obtained, is 995nm.

(Comparative examples A 6)

On one side lauryl sodium sulfate aqueous solution 100g is stirred with 20 ℃ of solution temperatures, 300rpm in beaker, Yi Bian drop into the mixing solutions 20g of 1.71w/w%PR-254/96.70w/w% DMSO 99.8MIN. (DMSO)/1.59w/w%8N potassium hydroxide aqueous solution.Obtain the pigment nanoparticle dispersion liquid.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and result, volume average particle size are 489nm.In addition, this pigment nanoparticle dispersion liquid was dialysed in pure water 24 hours, remove sodium lauryl sulphate, behind the DMSO etc., carry out drying, obtain pigment nanoparticle powder with dialysis tubing.This powder is dropped in the ion exchanged water again, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more, and median size is bigger than what in beaker, just obtained, is 985nm.

(Comparative examples A 7)

On one side with Disperbyk-190 (BYK Chemie society system) propylene glycol methyl ether acetate (PGMEA) solution 100g in beaker with 20 ℃ of solution temperatures; 300rpm stirs, Yi Bian drop into 2.55w/w%PR-254/76.55w/w% THF (THF)/0.77w/w% sodium ethylate/20.13w/w% alcoholic acid mixing solutions 20g.Obtain the pigment nanoparticle dispersion liquid.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and result, volume average particle size are 791nm.In addition, remove PGMEA, behind the THF etc., carry out drying, obtain pigment nanoparticle powder from this pigment nanoparticle dispersion liquid.This powder is dropped among the PGMEA again, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more, and volume average particle size is bigger than what in beaker, just obtained, is 1185nm.

The above shows; The reaction unit that use mixes in can be near the film fluid that each other subtend processing that set, that at least one side is rotated with respect to the opposing party forms between with face discretely equably and the pigment nanoparticle that obtains; Be the particulate of nano-scale, redispersibility is excellent simultaneously.

(embodiment A 8)

Secondly; Shown in Fig. 1 (A); Use is can be near the processing that set, that the relative the opposing party of at least one side is rotated of isolating subtend with face 1, evenly stir and the blended reaction unit in the formed film fluid between 2; Solution and the water phase surfactant mixture that will contain the Pigment red 177 (structure name: anthraquinone below is called PR-177) that in filter purposes etc., uses collaborate in the film fluid, one side uniform mixing the pigment nanoparticle is separated out.

To carry out liquor charging for 20 ℃ with supply pressure/back pressure 0.02MPa/0.01Mpa, rotating speed 100rpm, liquor charging temperature as the 1st fluidic Aqualon KH-10 (the first industrial pharmacy (strain) system) aqueous solution from central authorities on one side, will as 2nd fluidic 3.0w/w%PR-177/97.0w/w% concentrated sulfuric acid solution with 1ml/min import processing with face 1,2 between on one side.The pigment nanoparticle dispersion liquid is discharged from face from handling.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and result, volume average particle size are 17nm.In addition, this pigment nanoparticle dispersion liquid was dialysed in pure water 24 hours, remove Aqualon KH-10, behind the vitriol oil etc., carry out drying, obtain pigment nanoparticle powder with dialysis tubing.Again this powder is dropped in the ion exchanged water; Stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more; Volume average particle size is 17nm with identical with what just obtained after being discharged between face from handling.

The TEM photo of the pigment nanoparticle that obtains is shown in Figure 31.

(embodiment A 9)

Secondly, the solution and the water phase surfactant mixture that contain equally at pigment Green 7 that effects such as filter purposes are used (below be called PG-7) are collaborated in the film fluid, one side uniform mixing the pigment nanoparticle is separated out.

On one side will be as the 1st fluidic Aqualon KH-10 (the first industrial pharmacy (strain) system) aqueous solution to supply with pressure/back pressure 0.02MPa/0.01Mpa, rotating speed 500rpm from central authorities; The liquor charging temperature is carried out liquor charging for 20 ℃, will as 2nd fluidic 0.2w/w%PG-7/99.8w/w% concentrated sulfuric acid solution with 5ml/min import processing with face 1,2 between on one side.The pigment nanoparticle dispersion liquid is discharged from face from handling.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and result, volume average particle size are 12nm.In addition, this pigment nanoparticle dispersion liquid was dialysed in pure water 24 hours, remove Aqualon KH-10, behind the vitriol oil etc., carry out drying, obtain pigment nanoparticle powder with dialysis tubing.Again this powder is dropped in the ion exchanged water; Stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more; Volume average particle size is 12nm with identical with what just obtained after being discharged between face from handling.

(embodiment A 10)

Secondly, will contain use and in the film fluid, collaborate at solution and water phase surfactant mixture as the pigment Yellow 12 8 that uses in the jetting ink etc. (below be called PY-128), one side uniform mixing the pigment nanoparticle is separated out.

To carry out liquor charging for 20 ℃ with supply pressure/back pressure 0.05MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature as the 1st fluidic lauryl sodium sulfate aqueous solution from central authorities on one side, will as the mixing solutions of the 2nd fluidic 1.22w/w%PY-128/5.8w/w%8N-KOH aqueous solution/87.8w/w% DMSO 99.8MIN. (DMSO)/5.1w/w% ion exchanged water with 1ml/min import processing with face 1,2 between on one side.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and result, volume average particle size are 13nm.In addition, this pigment nanoparticle dispersion liquid was dialysed in pure water 24 hours, remove KOH, behind the DMSO etc., carry out drying, obtain pigment nanoparticle powder with dialysis tubing.Again this powder is dropped in the ion exchanged water; Stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more; Volume average particle size is 13nm with identical with what just obtained after being discharged between face from handling.The TEM photo of the pigment nanoparticle that obtains is shown in Figure 32.

(embodiment A 11)

Secondly, the solution and the water phase surfactant mixture that contain the Pigment red 170 that in jetting ink etc., uses (below be called PR-170) are equally collaborated in the film fluid, one side uniform mixing the pigment nanoparticle is separated out.

To carry out liquor charging for 20 ℃ with supply pressure/back pressure 0.05MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature as the 1st fluidic lauryl sodium sulfate aqueous solution from central authorities on one side, will as the mixing solutions of the 2nd fluidic 1.59w/w%PR-170/1.70w/w%8N-KOH aqueous solution/75.7w/w% DMSO 99.8MIN. (DMSO)/21.6w/w% ion exchanged water with 1ml/min import processing with face 1,2 between on one side.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and result, volume average particle size are 14nm.In addition, this pigment nanoparticle dispersion liquid was dialysed in pure water 24 hours, remove KOH, behind the DMSO etc., carry out drying, obtain pigment nanoparticle powder with dialysis tubing.Again this powder is dropped in the ion exchanged water; Stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more; Volume average particle size is 14nm with identical with what just obtained after being discharged between face from handling.

(Comparative examples A 8)

On one side Aqualon KH-10 (the first industrial pharmacy (strain) system) aqueous solution 100g is stirred with 20 ℃ of solution temperatures, 300rpm in beaker, Yi Bian drop into 3.0w/w%PR-177/97.0w/w% concentrated sulfuric acid solution 20g.Obtain the pigment nanoparticle dispersion liquid.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and result, volume average particle size are 442nm.In addition, this pigment nanoparticle dispersion liquid was dialysed in pure water 24 hours, remove Aqualon KH-10, behind the sulfuric acid etc., carry out drying, obtain pigment nanoparticle powder with dialysis tubing.This powder is dropped in the ion exchanged water again, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more, and volume average particle size is 992nm than big with what just obtained in the beaker.

(Comparative examples A 9)

On one side Aqualon KH-10 (the first industrial pharmacy (strain) system) aqueous solution 100g is stirred with 20 ℃ of solution temperatures, 300rpm in beaker, Yi Bian drop into 0.2w/w%PG-7/99.8w/w% concentrated sulfuric acid solution 20g.Obtain the pigment nanoparticle dispersion liquid.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and result, volume average particle size are 551nm.In addition, this pigment nanoparticle dispersion liquid was dialysed in pure water 24 hours, remove Aqualon KH-10, behind the sulfuric acid etc., carry out drying, obtain pigment nanoparticle powder with dialysis tubing.This powder is dropped in the ion exchanged water again, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more, and volume average particle size is 972nm than big with what just obtained in the beaker.

(Comparative examples A 10)

On one side lauryl sodium sulfate aqueous solution 100g is stirred with 20 ℃ of solution temperatures, 300rpm in beaker, Yi Bian drop into the mixing solutions 20g of the 1.22w/w%PY-128/5.8w/w%8N-KOH aqueous solution/87.8w/w% DMSO 99.8MIN. (DMSO)/5.1w/w% ion exchanged water.Obtain the pigment nanoparticle dispersion liquid.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and result, volume average particle size are 641nm.In addition, this pigment nanoparticle dispersion liquid was dialysed in pure water 24 hours, remove sodium lauryl sulphate, behind the DMSO etc., carry out drying, obtain pigment nanoparticle powder with dialysis tubing.This powder is dropped in the ion exchanged water again, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more, and volume average particle size is 1122nm than big with what just obtained in the beaker.

(Comparative examples A 11)

On one side lauryl sodium sulfate aqueous solution 100g is stirred with 20 ℃ of solution temperatures, 300rpm in beaker, Yi Bian drop into mixing solutions (pH＞16) 20g of the 1.59w/w%PR-170/1.70w/w%8N-KOH aqueous solution/75.7w/w% DMSO 99.8MIN. (DMSO)/21.6w/w% ion exchanged water.Obtain the pigment nanoparticle dispersion liquid.The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the pigment nanoparticle dispersion liquid that obtains, and result, volume average particle size are 448nm.In addition, this pigment nanoparticle dispersion liquid was dialysed in pure water 24 hours, remove sodium lauryl sulphate, behind the DMSO etc., carry out drying, obtain pigment nanoparticle powder with dialysis tubing.This powder is dropped in the ion exchanged water again, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains the pigment nanoparticle dispersion liquid once more, and volume average particle size is 968nm than big with what just obtained in the beaker.

The above shows; The reaction unit that use mixes in can be near the film fluid that each other subtend processing that set, that at least one side is rotated with respect to the opposing party forms between with face discretely equably and the pigment nanoparticle that obtains; Be the particulate of nano-scale, redispersibility is excellent simultaneously.

(B) metal supports carbon

Below, the reaction that generation metal of the present invention is supported carbon describes.

This reaction, like Fig. 1 (A) and meanwhile shown device, can near the processing that each other sets to subtend discretely, at least one side is rotated with respect to the opposing party with face 1, between 2 by the strong hand uniform mixing take place.

At first; From the 1st d1 of importing portion as 1 stream; To import as the aqueous solution that the 1st fluid makes carbon black dispersion be added with reductive agent can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with 1,2 in face, the film fluid that generation is made up of the 1st fluid between this processing is with face.

Then, from the 2nd d2 of importing portion, will as the 2nd fluidic reactant the aqueous solution or the colloidal dispersion of metal-salt as other stream, directly import in above-mentioned processing with face 1, the film fluid that constitutes by the 1st fluid that generated between 2.

As the metal that is contained in the above-mentioned aqueous solution or the colloidal dispersion, but illustration platinum, palladium, gold, silver, rhodium, iridium, ruthenium, osmium, cobalt, manganese, nickel, iron, chromium, molybdenum, titanium etc., preferred especially precious metal.

As stated; Can supply with to press and be applied to through fluidic the processing that is rotated with the pressure equilibrium of the pressure between the face with fixed distance processing with face 1, between 2; The 1st fluid and the 2nd fluid by moment ground mix; Through liquid phase reduction, generate the reaction that the metal that supports metal particle supports carbon on the sooty surface.

What explain is, owing to can carry out above-mentioned reaction with face 1, between 2 and get final product handling, therefore, also can import the 2nd fluid through the 1st d1 of importing portion on the contrary with above-mentioned, imports the 1st fluid through the 2nd d2 of importing portion.That is, the appellation of the what is called the 1st, the 2nd in each solvent is the n of the solvent of a plurality of existence of expression, and just also can there be the solvent more than the 3rd in the mark in order to discern.

Metal supports carbon and catalyst-loaded catalyst loading amount and the homogeneity of metal; And the particle diameter of the metal that supports; Can handle with the rotating speed of portion 10,20, above-mentioned each fluidic supply pressure through making, make above-mentioned each flow rate of fluid, Reynolds number, or processing with face 1, distance between 2, in addition; Through changing above-mentioned each concentration of fluid, regulate.In addition, can generate the particle diameter that even metal supports carbon, can regulate the metal that supports according to purpose.

Because the metal of above-mentioned generation supports carbon, take out from treatment unit with the cf-that face 1,2 produces with respect to the processing that the opposing party is rotated through at least one side, therefore do not need big pressure.In addition, treatment unit has oneself's discharge property thus, thus, does not have the obstruction of product, in addition according to the turnout of necessity, can use general amplification notion to carry out the maximization of body.

As stated; Remove the 1st d1 of importing portion; Beyond the 2nd d2 of importing portion, the 3rd d3 of importing portion also can be set, under this situation on treatment unit; For example can be from each importing portion, with the aqueous solution that is dispersed with the sooty aqueous solution, has added reductive agent, the aqueous solution or the colloidal dispersion of metal-salt are imported in the treatment unit respectively.Like this, can distinctly manage concentration, the pressure of each solution, can more critically control metal and support the reaction that carbon generates.Even under the situation that is provided with the importing portion more than the 4th, the fluid sectionalization that equally also can be so will import to treatment unit.

Secondly, the reaction that soccerballene nano whisker nanofiber-nanotube is generated describes.The soccerballene that uses as the present invention has C60 or a C70 as representative.

The crystallization that forms by soccerballene and the evolution reaction of soccerballene nano whisker nanofiber-nanotube; Manufacturing installation shown in Fig. 1 (A), can near the processing that set, that at least one side is rotated with respect to the opposing party of isolating subtend with face between, and meanwhile by the strong hand uniform mixing take place.

At first; From the 1st d1 of importing portion as 1 stream; To contain that to be dissolved with reactant be that the solution of the 1st solvent of soccerballene imports can be near the subtend configuration, that at least one side is rotated with respect to the opposing party each other processing discretely with 1,2 in face, the film fluid that generation is made up of the 1st fluid between this processing is with face.

Then, from the 2nd d2 of importing portion as other stream, the 2nd solvent that the solubleness of soccerballene is also littler than the 1st solvent directly imports the film fluid that is made up of the 1st fluid that is generated with 1,2 in face in above-mentioned processing.

Here; When use has been dissolved the solution of catalyzer in above-mentioned the 2nd solvent; This solution is not specially limited; Through having dissolved the solution of catalyzer more than a kind or a kind that is selected among Cu/ZnO/Al2O3, PtCl4, Cu, Ru/PtCl4, Ru, the Pt, make catalyst loading, can make the crystallization and the soccerballene nano whisker nanofiber-nanotube that form by fullerene molecule.

In addition; Even through the solution that uses the platinum derivatives that in the solution that contains the 1st solvent that is dissolved with soccerballene, adds soccerballene to obtain, also can be catalyst-loaded or in the soccerballene crystallization, contain catalyzer, make the crystallization and the soccerballene nano whisker nanofiber-nanotube that form by soccerballene.

As stated; Through fluidic supply pressure and the processing that is being rotated with face between applied pressure pressure equilibrium and with fixed distance processing with face 1, between 2; The solution that contains the 1st solvent is stirred with the 2nd solvent and mixes, the crystallization that can carry out being formed by soccerballene and the evolution reaction of soccerballene nano whisker nanofiber-nanotube.

What explain is, owing to can carry out above-mentioned reaction with face 1, between 2 and get final product handling, therefore, also can import the 2nd solvent from the 1st d1 of importing portion on the contrary with above-mentioned, contains the solution of the 1st solvent from the 2nd d2 of importing portion importing.That is, the appellation of the what is called the 1st, the 2nd in each solvent is the n of the solvent of a plurality of existence of expression, and just also can there be the solvent more than the 3rd in the mark in order to discern.

The length of the soccerballene nano whisker nanofiber-nanotube that obtains and the control of thickness can be through changing rotating speed, the flow velocity of handling with portion 10,20 and handling and regulate with face 1, the distance between 2, catalyzer, material concentration.

In addition, constitute the fullerene molecule of the soccerballene nano whisker nanofiber-nanotube that obtains, also can be bag soccerballene or fullerene derivate in the metal.

In addition, crystallization and nano whisker nanofiber-nanotube that the fullerene molecule that obtains constitutes can have the shape of sealing, also can have the shape of perforate.

What explain is that more detailed for above-mentioned catalyst loading, the crystallization that can form through the soccerballene that will generate as stated with vacuum furnace and soccerballene nano whisker nanofiber-nanotube heat and carry out.Particularly, heat from 300 ℃ to 1000 ℃.

As stated, remove the 1st d1 of importing portion, beyond the 2nd d2 of importing portion; The 3rd d3 of importing portion also can be set on treatment unit; Under this situation, for example can be from each importing portion, will contain solution, the 2nd solvent of the 1st solvent, the solution that contains the stablizer dispersion agent imports in the treatment unit respectively.Like this, but each the management each solution concentration, pressure, can more critically control evolution reaction.Even under the situation that is provided with the importing portion more than the 4th, the fluid sectionalization that equally also can be so will import to treatment unit.

Can in the soccerballene nano whisker nanofiber-nanotube that obtains as stated, mix synthetic resins and solvent and carry out moulding, use the film that obtains that the film/electrode linker of fuel cell is provided.

Secondly, use the manufacturing installation of soccerballene nano whisker nanofiber-nanotube of the present invention, also apparatus for forming hydrogen can be provided.

Above-mentioned manufacturing installation can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, between 2; Soccerballene nano whisker nanofiber-nanotube is generated; And, make the catalyst loading more than a kind or a kind that is selected among Cu/ZnO/Al2O3, PtCl4, Cu, Ru/PtCl4, Ru, the Pt.And in this manufacturing installation, above-mentioned catalyzer can adhere to through the soccerballene nano whisker nanofiber-nanotube that supports or in the soccerballene crystallization, contain catalyzer and obtains.And, handling,, hydrogen is produced through filling liq fuel or geseous fuel with face 1, between 2.As liquid fuel, can use methyl alcohol, hydroborate etc.As geseous fuel, available methane or butane etc.

The reaction that the present invention can provide control to make soccerballene nano whisker nanofiber-nanotube is easy to method of manufacture, manufacturing installation, reaches the apparatus for forming hydrogen that uses it; Therefore can stably make soccerballene nano whisker nanofiber-nanotube; In addition; Can be useful on the industry with soccerballene nano whisker nanofiber-nanotube batch processization.

Below, support carbon and soccerballene nano whisker nanofiber-nanotube disclosed embodiment describes in more detail for metal, still, the present invention is not limited to these embodiment.

What explain is; In following embodiment; So-called " from central authorities "; Refer to such an extent that be the meaning of " from the 1st d1 of importing portion " of treatment unit shown in above-mentioned, Fig. 1 (A), the 1st fluid is meant that the above-mentioned the 1st is processed liquid, that the 2nd fluid is meant is above-mentioned, treatment unit shown in Fig. 1 (A) " that import from the 2nd d2 of importing portion, above-mentioned the 2nd is processed liquid.

(Embodiment B 1)

Shown in Fig. 1 (A); Use can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, the reaction unit that mixes equably in the formed film fluid between 2; With dissolving as the fructose of reductive agent and also be dispersed with the sooty aqueous solution in the film fluid with the aqueous solution interflow of containing metallic compound, Yi Bian mixing supports metal particle through liquid phase reduction equably.

On one side will be as the 1st fluidic 2% carbon black (the system Ketjen Black EC of lion society)/ethanol/fructose dispersion liquid from central authorities; To supply with pressure/back pressure=0.30MPa/0.01Mpa, rotating speed 1000rpm, 80 ℃ of liquor chargings of liquor charging temperature; To import processing with between face with 10ml/min as the 2nd fluidic 5% dinitrobenzene diamines platinum nitrate solution on one side.The platinum particle dispersion liquid that on the sooty surface, supports is discharged from face from handling.

By tem observation, confirm the platinum particulate about particle diameter 1nm on the carbon particles by high dispersive support.In addition, the platinum loading is 48%.

(Embodiment B 2)

On one side will be as the 1st fluidic 2% carbon black (the system Ketjen Black EC of lion society)/ethanol/fructose dispersion liquid from central authorities; To supply with pressure/back pressure=0.20MPa/0.01Mpa, rotating speed 1000rpm, 80 ℃ of liquor chargings of liquor charging temperature; To import processing with between face with 10ml/min as the 2nd fluidic 5% dinitrobenzene diamines platinum nitrate solution on one side.The platinum particle dispersion liquid that on the sooty surface, supports is discharged from face from handling.

By tem observation, confirm the platinum particulate about particle diameter 1nm on the carbon particles by high dispersive support.In addition, the platinum loading is 44%.

(Embodiment B 3)

On one side will be as the 1st fluidic 2% carbon black (the system Ketjen Black EC of lion society)/ethanol/fructose dispersion liquid from central authorities; To supply with pressure/back pressure)=0.20MPa/0.01Mpa, rotating speed 2000rpm, 80 ℃ of liquor chargings of liquor charging temperature; To import processing with between face with 10ml/min as the 2nd fluidic 5% dinitrobenzene diamines platinum nitrate solution on one side.The platinum particle dispersion liquid that on the sooty surface, supports is discharged from face from handling.

By tem observation, confirm the platinum particulate about particle diameter 1nm on the carbon particles by high dispersive support.In addition, the platinum loading is 40%.

(Embodiment B 4)

On one side will be as the 1st fluidic 2% carbon black (the system Ketjen Black EC of lion society)/ethanol/fructose dispersion liquid from central authorities; To supply with pressure/back pressure=0.10MPa/0.01Mpa, rotating speed 2000rpm, 80 ℃ of liquor chargings of liquor charging temperature; To import processing with between face with 10ml/min as the 2nd fluidic 5% dinitrobenzene diamines platinum nitrate solution on one side.The platinum particle dispersion liquid that on the sooty surface, supports is discharged from face from handling.

By tem observation, confirm the platinum particulate about particle diameter 1nm on the carbon particles by high dispersive support.In addition, the platinum loading is 40%.

(comparative example B1)

With 2% carbon black (the system Ketjen Black EC of lion society)/ethanol/fructose water solution 100g, beaker in solution temperature 80 ℃, 300rpm stir on one side, drop into 5% dinitrobenzene diamines platinum nitrate solution 20g on one side.Obtain the platinum particle dispersion liquid that on the sooty surface, supports.By tem observation, confirm to be supported unevenly at the platinum particulate about particle diameter 5～15nm on the carbon particles.In addition, the platinum loading is 12%.

(Embodiment B 5)

As shown in Figure 1; Use the crystallization of fullerene molecule formation and the manufacturing installation of soccerballene nano whisker nanofiber-nanotube; Can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, drop into Virahol (IPA) between 2; To be dissolved in soccerballene (C60) the toluene from other stream and directly put into and handle,, mix equably with film fluidic state with in face 1, the film fluid between 2.Surface reaction in being stirred the film fluid that has mixed by the strong hand is very fast, but mass production.

(Embodiment B 6)

The same with Embodiment B 5; Use the manufacturing installation of soccerballene nano whisker nanofiber-nanotube; Replace Virahol (IPA) with the material that is dissolved in the catalyzer that has dissolved PtCl4, Ru/PtCl4 in the Virahol (IPA); The same with Embodiment B 1, can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, surface reaction takes place between 2.The soccerballene nano whisker nanofiber-nanotube that obtains is heated with 300 ℃ to 1000 ℃ temperature with vacuum furnace.Can obtain Pt, soccerballene nano whisker nanofiber-nanotube that Ru/Pt, catalyzer have been supported.The soccerballene nano whisker nanofiber-nanotube that generates has high surface area.

(Embodiment B 7)

At the Pt that Embodiment B 6 obtains, in the manufacturing installation that soccerballene nano whisker nanofiber-nanotube that Pt/Ru has been supported has adhered to, fill methyl alcohol.As temperature being brought up to 200 to 600 ℃, the bubble generation of hydrogen.

(Embodiment B 8)

At the Pt that Embodiment B 6 obtains, add polymer electrolyte and solvent in soccerballene nano whisker nanofiber-nanotube that Ru/Pt, catalyzer have been supported, make paste, it is carried out silk screen printing, make its drying.Here, use nafion as polymer electrolyte, as the glycol dimethyl ether of solvent, and the organic solvent of n-butyl acetate.The tunicle that obtains can form film/electrode linker (MEA structure) and utilize as the parts of high-molecular electrolyte fuel battery.

(C) metal particle

Below, the generation of the particulate of the reduction reaction of utilizing metallic compound of the present invention is described.

This reaction, Fig. 1 (A) shown device, can be near each other subtend sets discretely, at least one side is rotated with respect to the opposing party processing with face 1, between 2, on one side one side uniform mixing takes place by the strong hand.

At first; From the 1st d1 of importing portion as 1 stream; To contain macromolecule dispersing agent and reactant is the aqueous solution of metallic compound as the 1st fluidic; Importing can be near each other the subtend configuration, that at least one side is rotated with respect to the opposing party processing discretely with 1,2 in face, the film fluid that generation is made up of the 1st fluid between this processing is with face.

Then, from the 2nd d2 of importing portion, will directly import the above-mentioned film fluid that constitutes by the 1st fluid as the 2nd fluidic reductive agent aqueous solution as other stream.

As stated; Through fluidic supply pressure and the processing that is being rotated with face between applied pressure pressure equilibrium and with fixed distance processing with face 1, between 2; The 1st fluid and the 2nd fluid interflow are on one side one side uniform mixing carries out reduction reaction in the film fluid.And the colloidal metal solution that contains the metal particle that has been reduced is discharged from from device.

What explain is, owing to can carry out above-mentioned reaction with face 1, between 2 and get final product handling, therefore, also can import the 2nd fluid from the 1st d1 of importing portion on the contrary with above-mentioned, imports the 1st fluid from the 2nd d2 of importing portion.That is, the appellation of the what is called the 1st, the 2nd in each solvent is the n of the solvent of a plurality of existence of expression, and just also can there be the solvent more than the 3rd in the mark in order to discern.

The control of the particle diameter of the metal particle that obtains, single dispersity of colloidal metal solution can be regulated with face 1, distance and film flow rate of fluid between 2, material concentration through change handling rotating speed with face 1,2, processing.

Metal particle through the present invention obtains is high crystalline, and redispersibility is also good, and volume average particle size is 1～200nm, and the CV value in the size-grade distribution of metal particle is 5～40%, is preferably 10～20%.

The metallic element that metallic compound contained, that form above-mentioned metal particle that in the method for manufacture of metal particle of the present invention, uses is not done special qualification, preferred precious metal or copper.Precious metal does not limit especially, for example can enumerate gold, silver, ruthenium, rhodium, palladium, osmium, iridium, platinum etc.Wherein preferred gold, silver, platinum, palladium.And, for iron, nickel, chromium, manganese, aluminium, molybdenum, niobium, the monomer of representing in tantalum etc., the chemical periodictable, normal temperature state show the element of metal rerum natura down, can use above-mentioned method of manufacture.

Above-mentioned metallic compound is not done special qualification yet, for example, can be the sour tetrahydrate of tetrachloro gold (III) (hydrochloro-auric acid), the sulfurous acid gold; Potassium aurate, Silver Nitrate, silver acetate, silver perchlorate (IV); Chlordene platinum (IV), sour hexahydrate (chlorination platinic acid), chlorination potassium platinate, cupric chloride (II) duohydrate; Venus crystals (II) monohydrate, copper sulfate (II), Palladous chloride (II) duohydrate, Trichlororhodium (III) trihydrate etc.These metallic compounds can be also with using more than a kind or 2 kinds.

As above-mentioned solvent,, for example, can enumerate water, organic solvent etc. as long as the above-mentioned metallic compound of solubilized is not just done special qualification.As above-mentioned organic solvent, do not do special qualification yet, for example, can enumerate ethanol, the alcohol of the carbon number 1～4 of terepthaloyl moietie etc., the ketone of acetone etc., the ester class of acetate ethyl etc.Above-mentioned solvent can use more than a kind or 2 kinds.Be under the situation of mixture of water and organic solvent at above-mentioned solvent,, for example can enumerate acetone, methyl alcohol, ethanol, terepthaloyl moietie etc. as the solvent of above-mentioned organic solvent preferably water solubility.Among the present invention, consider preferably water, alcohol, and the mixing solutions of water and alcohol from the deliquescent aspect of above-mentioned metallic compound.

As the reductive agent that can use in the present invention; Though in the reaction system of liquid phase, can use ion through the reducing metal element to form any of various reductive agents that metal particle separates out; But after in the presence of the dispersion agent stated; Metallic compound and reductive agent; In can be, carry out reduction reaction, needn't give very big heat energy thus near the film fluid that each other subtend ground processing that set, that at least one side is rotated with respect to the opposing party forms between with face discretely, can future the metals ion of self-metallization compound be reduced to metal.

Reduction reaction in the above-mentioned forced ultra-thin film rotating uniform mixing reaction method is set and will be handled with face and directly carry out temperature regulation, may command temperature of reaction through importing the fluidic temperature.

As reductive agent, for example, the Peng Qinghuana of can giving an example, inferior sodium phosphate, hydrazine, ion of transition metal (tervalent titanium ion, the cobalt ion of divalence etc.) and methyl alcohol; Ethanol, the alcohol of 2-propyl alcohol etc., or xitix etc., in addition, can enumerate terepthaloyl moietie, gsh; Organic acid (Hydrocerol A, oxysuccinic acid, tartrate etc.), reductibility carbohydrate (glucose, semi-lactosi, seminose; Fructose, sucrose, SANMALT-S, raffinose, stachyose etc.), and glycitols or Sorbitol Powder etc.In addition, also can use amine, as associated amines, for example can enumerate: propylamine, butylamine, hexylamine, diethylamine, dipropyl amine, dimethylethyl amine as reductive agent; Diethylmethyl amine, triethylamine, quadrol, N,N,N, 1,3-diaminopropanes; N, N, N ', N '-tetramethyl--1,3-diaminopropanes, Triethylenetetramine (TETA), the fatty amine of tetren etc., piperidines; The N-methyl piperidine, piperazine, N, N '-lupetazin, tetramethyleneimine, N-crassitude, the ester ring type amine of morpholine etc., aniline; Methylphenylamine, N, accelerine, Tolylamine, methyl oxyaniline, the aromatic amine of phenetidine etc., benzylamine, N-methylbenzylamine; N, N-dimethyl benzylamine, phenylethylamine, phenylenediamine, N, N, N ', the aralkylamine of N '-tetramethyl-benzene diamines etc. etc.In addition, as above-mentioned amine, for example, also can enumerate methylamine ethanol, dimethyl amine ethanol; Trolamine, thanomin, diethylolamine, methyldiethanolamine, Propanolamine; 2-(3-amino propyl amino) ethanol, butanolamine, n-hexyl alcohol amine, the alkanolamine of dimethylamino propyl alcohol etc.Wherein, preferred alkanolamine, more preferably dimethylethanolamine.

As dispersion agent, can use to solution have good solubility, simultaneously can be with the metal particle of separating out any of the various dispersion agents of dispersive well in solution.As above-mentioned dispersion agent, can use various dispersion agents, for example; Can enumerate polymine, the dispersion agent of the amine system of Vinylpyrrolidone polymer etc., ROHM; The macromolecule dispersing agent that has the hydrocarbon system of carbonyldioxy in the molecule of CMC 99.5 etc.; Poval (Z 150PH), or the multipolymer etc. of polyethyleneimine: amine moiety and polyethylene oxide part is arranged in 1 molecule, have the macromolecule dispersing agent of polar group.In addition, its molecular weight is preferably below 100000.In addition, also can use commercially available dispersion agent.As above-mentioned commercially available article, for example can enumerate Solsperse 20000, Solsperse24000, Solsperse 26000, and Solsperse 27000, and Solsperse 28000; Solsperse 41090 (above, Avecia society system), Disperbyk 160, and Disperbyk 161, and Disperbyk 162, and Disperbyk 163, and Disperbyk 166; Disperbyk 170, and Disperbyk 180, and Disperbyk 181, and Disperbyk 182, and Disperbyk 183, and Disperbyk 184; Disperbyk 190, and Disperbyk 191, and Disperbyk 192, and Disperbyk 2000, Disperbyk 2001 (above, BYK Chemie society system); Polymer100, Polymer 120, and Polymer 150, and Polymer 400, and Polymer 401; Polymer402, Polymer 403, and Polymer 450, and Polymer 451, and Polymer 452; Polymer453, EFKA-46, EFKA-47, EFKA-48, EFKA-49; EFKA-1501, EFKA-1502, EFKA-4540, EFKA-4550 (above, EFKA Chemical society system), FLOWLEN DOPA-158; FLOWLEN DOPA-22, FLOWLEN DOPA-17, FLOWLEN G-700, FLOWLEN TG-720W, FLOWLEN-730W; FLOWLEN-740W, FLOWLEN-745W (above, common prosperity society chemistry system), AJISPER PA111, AJISPER PB711, AJISPER PB811; AJISPER PB821, AJISPER PW911 (above, aginomoto society system), JONCRYL678, JONCRYL 679, JONCRYL 62 (above, Johns on Polymer society system) etc.These dispersion agents can use separately, also can more than 2 kinds and use.

This dispersion agent owing to be for the metal particle of having separated out as stated dispersive material well in solution, also can mix with above-mentioned the 1st fluid and the arbitrary fluid of the 2nd fluidic.In addition; Be described below; Also can be in the processing that can set near isolating mutual subtend, at least one side is rotated with respect to the opposing party with face 1, importing only contain the aqueous solution of dispersion agent between 2, in the film fluid, in above-mentioned the 1st fluid and the 2nd fluidic two sides, mix.

As stated; Remove the 1st d1 of importing portion; Beyond the 2nd d2 of importing portion, the 3rd d3 of importing portion also can be set, under this situation on treatment unit; For example can be from each importing portion, will contain the aqueous solution of macromolecule dispersing agent, the aqueous solution that contains metallic compound, the reductive agent aqueous solution and import in the treatment unit respectively.Like this, but each manages concentration, the pressure of each solution, can more critically control the reaction that metal particle generates.Even under the situation that is provided with the importing portion more than the 4th, the fluid sectionalization that equally also can be so will import to treatment unit.

What explain is; As reduction reaction of the present invention; Except above-mentioned, each is handled and to process with conductive material with face, also can use to be utilized in above-mentioned each and to handle with additional electrical potential difference between face, manage with the electrochemical method of reducing of giving and accepting that carries out electronics between face throughout.

Below, enumerate embodiment for the reduction reaction of metallic compound and describe in more detail, still, the present invention is not limited to these embodiment.

What explain is; In following embodiment; So-called " from central authorities "; Refer to such an extent that be the meaning of " from the 1st d1 of importing portion " of treatment unit shown in above-mentioned, Fig. 1 (A), the 1st fluid is meant that the above-mentioned the 1st is processed liquid, that the 2nd fluid is meant is above-mentioned, treatment unit shown in Fig. 1 (A) " that import from the 2nd d2 of importing portion, above-mentioned the 2nd is processed liquid.

Shown in Fig. 1 (A); Use can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, the reaction unit that mixes equably in the formed film fluid between 2; Make contain metallic compound the aqueous solution in above-mentioned film fluid with the aqueous solution of dispersion agent and reductive agent interflow, Yi Bian evolution reaction is carried out in mixing equably.

(Embodiment C 1)

On one side will be as the 1st fluidic 10% hydrazine aqueous solution from central authorities; To supply with pressure/back pressure=0.02MPa/0.01Mpa, rotating speed 1000rpm, 80 ℃ of liquor chargings of liquor charging temperature; To just use on one side ammoniacal liquor be modulated into pH value be 20% Silver Nitrate/2% Vinylpyrrolidone polymer (molecular weight 20000) aqueous solution of 12 as the 2nd fluid, import processing with face 1, between 2 with 10ml/min.Has xanchromatic plasma body (plasmon) silver colloidal solution that absorb, water system from handling with face 1, being discharged between 2.Even the solution that is discharged from is kept in the Glass Containers, can not form silver-colored film at the container wall yet, silver mirror reaction can not appear.

Secondly, with the silver colloidal solution spinning that obtains, remove the operation of the impurity also lighter repeatedly than silver-colored particulate; Then; After cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of having used laser Doppler method the size-grade distribution of silver-colored particulate to be measured the result; Volume average particle size is 4.4nm, and the CV value of its size-grade distribution is 13%.And the yield of this silver particles is 95%.

(Embodiment C 2)

On one side will be as the 1st fluidic 10% hydrazine aqueous solution from central authorities; To supply with pressure/back pressure=0.10MPa/0.01Mpa, rotating speed 2000rpm, 80 ℃ of liquor chargings of liquor charging temperature; To just use on one side ammoniacal liquor be modulated into pH be 20% Silver Nitrate/2% Vinylpyrrolidone polymer (molecular weight 20000) aqueous solution of 12 as the 2nd fluid, import with 10ml/min and to handle with face 1, between 2.Has xanchromatic plasma body silver colloidal solution that absorb, water system from handling with face 1, being discharged between 2.Even the solution that is discharged from is kept in the Glass Containers, can not form silver-colored film at the container wall yet, silver mirror reaction can not appear.

Secondly, with the silver colloidal solution spinning that obtains, remove the operation of the impurity also lighter repeatedly than silver-colored particulate; Then; After cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of having used laser Doppler method the size-grade distribution of silver-colored particulate to be measured the result; Volume average particle size is 8.8nm, and the CV value of its size-grade distribution is 18%.And the yield of this silver particles is 91%.The TEM photo of the silver particles that obtains is shown among Figure 33.Interfere line observation to confirm as the high particle of crystallinity by particle.

(Embodiment C 3)

On one side will be as the 1st fluidic 10% dimethylaminoethanol (DMAE) aqueous solution from central authorities; To supply with pressure/back pressure=0.02MPa/0.02Mpa, rotating speed 1000rpm, 80 ℃ of liquor chargings of liquor charging temperature; To just use on one side ammoniacal liquor be modulated into pH value be 20% Silver Nitrate/2%BYK-190 (BYK Chemie society system) aqueous solution of 12 as the 2nd fluid, import processing with face 1, between 2 with 10ml/min.Has xanchromatic plasma body silver colloidal solution that absorb, water system from handling with face 1, being discharged between 2.Even the solution that is discharged from is kept in the Glass Containers, can not form silver-colored film at the container wall yet, silver mirror reaction can not appear.

Secondly, with the silver colloidal solution spinning that obtains, remove the operation of the impurity also lighter repeatedly than silver-colored particulate; Then; After cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of having used laser Doppler method the size-grade distribution of silver-colored particulate to be measured the result; Volume average particle size is 8.1nm, and the CV value of its size-grade distribution is 15%.And the yield of this silver particles is 82%.

(Embodiment C 4)

On one side will be as the 1st fluidic 10%DMAE aqueous solution from central authorities; To supply with pressure/back pressure=0.02MPa/0.01Mpa, rotating speed 1000rpm, 80 ℃ of liquor chargings of liquor charging temperature; To just use on one side ammoniacal liquor be modulated into pH value be 20% Silver Nitrate/2%BYK-190 (BYK Chemie society system) aqueous solution of 12 as the 2nd fluid, import processing with face 1, between 2 with 10ml/min.Silver colloidal solution with water system that the xanchromatic plasma body absorbs is from handling with face 1, being discharged between 2.Even the solution that is discharged from is kept in the Glass Containers, can not form silver-colored film at the container wall yet, silver mirror reaction can not appear.

Secondly, with the silver colloidal solution spinning that obtains, remove the operation of the impurity also lighter repeatedly than silver-colored particulate; Then; After cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of having used laser Doppler method the size-grade distribution of silver-colored particulate to be measured the result; Volume average particle size is 9.7nm, and the CV value of its size-grade distribution is 25%.And the yield of this silver particles is 88%.

(Embodiment C 5)

On one side will be as the 1st fluidic 10% hydrazine aqueous solution from central authorities; To supply with pressure/back pressure=0.02MPa/0.01Mpa, rotating speed 1000rpm, 80 ℃ of liquor chargings of liquor charging temperature; To just use on one side ammoniacal liquor be modulated into pH value be 20% Silver Nitrate/18% cupric nitrate/2%BYK-190 (BYK Chemie society system) aqueous solution of 12 as the 2nd fluid, import processing with face 1, between 2 with 10ml/min.The silver of water system, the colloidal solution of copper or yellow gold is from handling with face 1, being discharged between 2.Even the solution that is discharged from is kept in the Glass Containers, can not form silver-colored film at the container wall yet, silver mirror reaction can not appear.

Secondly, with the colloidal metal solution spinning that obtains, remove the operation of the impurity also lighter repeatedly than particulate; Then; After cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of having used laser Doppler method the size-grade distribution of particulate to be measured the result; Volume average particle size is 8.3nm, and the CV value of its size-grade distribution is 13%.In addition, silver ions and cupric ion to cooperate ratio (atomicity than) be 10: 9.And should silver, the yield of copper or yellow gold particle is 94%.

(Embodiment C 6)

On one side will be as the 1st fluidic 10%DMAE aqueous solution from central authorities; To supply with pressure/back pressure=0.02MPa/0.02Mpa, rotating speed 1000rpm, 80 ℃ of liquor chargings of liquor charging temperature; To just use on one side ammoniacal liquor be modulated into pH value be 20% Silver Nitrate/18% cupric nitrate/2%BYK-190 (BYK Chemie society system) aqueous solution of 12 as the 2nd fluid, import processing with face 1, between 2 with 10ml/min.The colloidal solution of the silver of water system, copper or yellow gold is from handling with face 1, being discharged between 2.Even the solution that is discharged from is kept in the Glass Containers, can not form silver-colored film at the container wall yet, silver mirror reaction can not appear.

Secondly, with the colloidal metal solution spinning that obtains, remove the operation of the impurity also lighter repeatedly than particulate; Then; After cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of having used laser Doppler method the size-grade distribution of particulate to be measured the result; Volume average particle size is 9.9nm, and the CV value of its size-grade distribution is 15%.And, silver ions and cupric ion to cooperate ratio (atomicity than) be 10: 9.And should silver, the yield of copper or yellow gold particle is 90%.

(comparative example C1)

, in beaker, stir on one side with 80 ℃ of solution temperatures, 300rpm with 10% hydrazine aqueous solution 20g, on one side will just to use ammoniacal liquor to be modulated into pH value be 20% Silver Nitrate/2% Vinylpyrrolidone polymer (molecular weight 20000) aqueous solution 20g input of 12.Obtain the silver colloidal solution of water system.But, if the solution that is discharged from is kept in the container of glass property, can form silver-colored film at the container wall, silver mirror reaction appears.

Secondly, with the silver colloidal solution spinning that obtains, remove the operation of the impurity also lighter repeatedly than particulate; Then; After cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of having used laser Doppler method the size-grade distribution of silver-colored particulate to be measured the result; Volume average particle size is 230nm, and the CV value of its size-grade distribution is 120%.

(comparative example C2)

, in beaker, stir on one side with 80 ℃ of solution temperatures, 300rpm with 10%DMAE aqueous solution 20g, on one side will just to use ammoniacal liquor to be modulated into pH value be 20% Silver Nitrate/18% cupric nitrate/2%BYK-190 (BYK Chemie society system) aqueous solution 20g input of 12.Obtain the silver of water system, copper or yellow gold colloidal solution.But,, form the film of silver and copper at the container wall if the solution that is discharged from is kept in the container of glass property.

Secondly, with the colloidal metal solution spinning that obtains, remove the operation of the impurity also lighter repeatedly than particulate; Then; After cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of having used laser Doppler method the size-grade distribution of particulate to be measured the result; Volume average particle size is 300nm, and the CV value of its size-grade distribution is 140%.Neck watt, silver ions and cupric ion to cooperate ratio (atomicity compares) be 10: 3.And should silver, the yield of copper or yellow gold particle is 9%.

The above results is shown in Table 2.What explain is that embodiment 1～6 in the table and comparative example 1～2 are represented the foregoing description C1～C6 and comparative example C1～C2 respectively.

(Embodiment C 7)

On one side will be as the 1st fluidic sodium borohydride/BYK-190/0.1N NaOH aqueous solution from central authorities; With supply pressure/back pressure=0.05MPa/0.01MPa, rotating speed 1140rpm, 45 ℃ of liquor chargings of liquor charging temperature, on one side will be as the sour hexahydrate of the 2nd fluidic chlordene platinum (IV)/BYK-190/1.0N H ₂SO ₄The aqueous solution imports processing with face 1, between 2 with 6ml/min.The platinum colloidal solution of water system is from handling with face 1, being discharged between 2.With the platinum colloidal solution that obtains; With the condition spinning of 1,000,000 G * 10 minute, the operation of removing the impurity also lighter repeatedly than platinum particulate, then; After cleaning with pure water; Use has been used the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of laser Doppler method the size-grade distribution of platinum particulate has been measured, and result, volume average particle size are 4.2nm.In addition, use dialysis tubing to remove BYK-190, sodium borohydride this platinum colloidal solution after, carry out drying, obtain platinum particulate powder.This powder is dropped in ion exchanged water again, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains platinum colloidal solution once more, and volume average particle size from processing identical with the face discharge, is 4.2nm with just.In addition, even under the situation with the platinum particulate powder redispersion in toluene that obtains, same median size also is 4.2nm.The TEM photo of the platinum particulate that obtains is shown in Figure 34 and Figure 35.

(Embodiment C 8)

On one side will be as the 1st fluidic sodium borohydride/BYK-190/0.1N NaOH aqueous solution from central authorities; To supply with pressure/back pressure=0.01MPa/0.005Mpa, rotating speed 600rpm, 55 ℃ of liquor chargings of liquor charging temperature; To import processing with face 1, between 2 with 8ml/min as the 2nd fluidic Tetrachloroplatinum/acid chloride/BYK-190/ acetone solution on one side.The platinum of water system-palldium alloy colloidal solution is from handling with face 1, being discharged between 2.With the platinum that obtains-palldium alloy colloidal solution; With the condition spinning of 1,000,000 G * 10 minute, remove operation repeatedly, then than platinum-impurity that the palldium alloy particulate is also light; After cleaning with pure water; Use has been used the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of laser Doppler method the size-grade distribution of platinum-palldium alloy particulate has been measured, and result, volume average particle size are 5.1nm.In addition, use dialysis tubing to remove BYK-190 in this platinum-palldium alloy colloidal solution, behind the sodium borohydride etc., carry out drying, obtain platinum-palldium alloy particulate powder.Again this powder is dropped in the ion exchanged water; Stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains platinum-palldium alloy colloidal solution once more; Volume average particle size is identical with what discharge between face from handling with just, is 5.1nm.In addition, even under the situation with the platinum that obtains-palldium alloy particulate powder redispersion in toluene, same median size also is 5.1nm.The TEM photo of gained platinum-palldium alloy particulate is shown in Figure 36 and Figure 37.Utilizing the result of the surface analysis of TEM-EDX analysis is that the ratio of platinum (Pt) and palladium (Pd) is Pt: Pd=73: 27 (mol%).The result of ICP luminescence analysis is that the ratio of platinum (Pt) and palladium (Pd) is Pt: Pd=77: 23 (mol%).From above content check, the particulate that obtains is the alloy particle of platinum-palladium.

(Embodiment C 9)

On one side will be as the 1st fluidic hydrazine/BYK-190 aqueous solution from central authorities; To supply with pressure/back pressure=0.04MPa/0.03Mpa, rotating speed 290rpm, 85 ℃ of liquor chargings of liquor charging temperature; To import processing with face 1, between 2 with 10ml/min as the 2nd fluidic cupric nitrate duohydrate aqueous solution on one side.The copper colloidal solution of water system is from handling with face 1, being discharged between 2.Even the solution that is discharged from is kept in the container of glass property, also can form copper film at the container wall.With the copper colloidal solution that obtains, with the condition spinning of 1,000,000 G * 10 minute, the operation of removing the impurity also lighter repeatedly than copper particulate.Then, after cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of having used laser Doppler method that the size-grade distribution of copper particulate is measured, result, volume average particle size are 4.4nm.And, use dialysis tubing to remove BYK-190 this copper particle dispersion liquid, behind the hydrazine etc., carry out drying, obtain copper particulate powder.This powder is dropped in the ion exchanged water again, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains copper fine particle dispersion once more, and volume average particle size is identical with what discharge between face from handling with just, is 4.4nm.

(Embodiment C 10)

On one side will be as the 1st fluidic 5.5% hydrazine/2.75%Disperbyk BYK-190 aqueous solution from central authorities; To supply with pressure/back pressure=0.02MPa/0.05Mpa, rotating speed 1000rpm, 25 ℃ of liquor chargings of liquor charging temperature; To import processing with face 1, between 2 with 2ml/min as the 2nd fluidic 35% nickel sulfate hexahydrate compound/2.77%Disperbyk BYK-190 aqueous solution on one side.The nickel particle solution of water system is from handling with face 1, being discharged between 2.What explain is, is used to make the water of the aqueous solution, be carry out the nitrogen bubbling, carry out deoxidation exchange of particles water.

Secondly, with the nickel colloidal solution that obtains, use ultracentrifuge (BECKMAN COULTER society system, Optima ^TMMAX-XP Ultracentrifuge), with the condition spinning of 400000G * 20 minute, the operation of removing the impurity also lighter repeatedly than nickel particle.Then, after cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA-EX150 of day machine dress strain (strain) system) of having used laser Doppler method that the size-grade distribution of nickel particle is measured, result, volume average particle size are 4.2nm.

With the nickel particle dispersion liquid lyophilize that obtains; The nickel particle powder that obtains is passed through X-ray diffraction device (the tortuous device of full-automatic many purposes X ray of PANalytivacl society system; X ' Pert PRO MPD) resolve, the nickel particle that results verification obtains is noncrystalline.That is, in the application's invention, both can as above-mentioned Embodiment C 2, make the metal particle of high crystalline, the amorphous metal particle that also can as this Embodiment C 10, make.

The noncrystalline particulate powder of the above-mentioned nickel that obtains is mixed in toluene, use the sono-cleaner redispersion.By the particle size distribution results verification: volume average particle size is 4.1nm, and the redispersibility of the noncrystalline particulate of nickel that obtains is good.

The TEM photo of the nickel particle that obtains is shown in Figure 38.

(comparative example C3)

With sodium borohydride/BYK-190/0.1N NaOH aqueous solution 100g, in beaker, stir, on one side on one side with the sour hexahydrate of chlordene platinum (IV)/BYK-190/1.0N H with 45 ℃ of solution temperatures, 300rpm ₂SO ₄Aqueous solution 20g drops into.Obtain platinum colloidal solution.With the platinum colloidal solution spinning that obtains, the operation of removing the impurity also lighter repeatedly than platinum particulate.Then, after cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of having used laser Doppler method that the size-grade distribution of platinum particulate is measured, result, volume average particle size are 645nm.

(comparative example C4)

With sodium borohydride/BYK-190/0.1N NaOH aqueous solution 100g, in beaker, stir on one side with 55 ℃ of solution temperatures, 300rpm, on one side Tetrachloroplatinum/acid chloride/BYK-190/ acetone solution 20g is dropped into.Obtain platinum-palldium alloy colloidal solution.With the platinum that obtains-palldium alloy colloidal solution spinning, remove operation repeatedly than platinum-impurity that the palldium alloy particulate is also light.Then, after cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of having used laser Doppler method that the size-grade distribution of platinum-palldium alloy particulate is measured, result, volume average particle size are 756nm.In addition, this platinum-palldium alloy colloidal solution removed BYK-190, sodium borohydride etc. with dialysis tubing after, carry out drying, obtain platinum-palldium alloy particulate powder.This powder is dropped in the ion exchanged water again, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains platinum-palldium alloy colloidal solution once more, and volume average particle size is bigger than what from beaker, just obtained, is 881nm.

(comparative example C5)

With hydrazine/BYK-190 aqueous solution 100g, in beaker, stir on one side with 85 ℃ of solution temperatures, 300rpm, on one side cupric nitrate duohydrate aqueous solution 20g is dropped into.Obtain copper colloidal solution.With the copper colloidal solution spinning that obtains, the operation of removing the impurity also lighter repeatedly than copper particulate.Then, after cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of having used laser Doppler method that the size-grade distribution of copper particulate is measured, result, volume average particle size are 756nm.In addition, this colloidal solution removed BYK-190, hydrazine etc. with dialysis tubing after, carry out drying, obtain copper particulate powder.This powder is dropped in the ion exchanged water again, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system), the result obtains copper colloidal solution once more, and volume average particle size is bigger than what from beaker, just obtained, is 944nm.

The above shows; The reaction unit that use mixes in can be near the film fluid that each other subtend processing that set, that at least one side is rotated with respect to the opposing party forms between with face discretely equably and the pigment nanoparticle that obtains; Be the particulate of nano-scale, redispersibility is excellent simultaneously.

(comparative example C6)

With 5.5% hydrazine/2.75%Disperbyk BYK-190 aqueous solution 100ml, in beaker, stir on one side with 25 ℃ of solution temperatures, 300rpm, on one side 35% nickel sulfate hexahydrate compound/2.77%Disperbyk BYK-190 aqueous solution 1ml is dropped into.Obtain the nickel colloidal solution of water system.

Secondly, with the nickel colloidal solution that obtains, use ultracentrifuge (BECKMAN COULTER society system, Optima ^TMMAX-XP Ultracentrifuge), with the condition spinning of 400000G * 20 minute, the operation of removing the impurity also lighter repeatedly than nickel particle.Then, after cleaning with pure water, use the particle size distribution device (the trade(brand)name microtrac UPA-EX150 of day machine dress strain (strain) system) of having used laser Doppler method that the size-grade distribution of nickel particle is measured, result, volume average particle size are 199.2nm.

Nickel particle dispersion liquid lyophilize with obtaining mixes the nickel particle powder that obtains in toluene, use the sono-cleaner redispersion.By the particle size distribution result, volume average particle size is bigger than what from beaker, just obtained, is 311.6nm.

(D) biological uptake thing particulate

Below, the concrete mode of biological uptake thing particulate method of manufacture is described.At first, the method that for the variation through solubility biological uptake thing particulate is separated out is described.

In the film fluid that between the processing of the above-mentioned device of having explained is with face, forms; To contain the solution that to be dissolved with at least a kind of micronize object material be the 1st solvent of biological uptake thing particulate starting material; Mix with the solvent that can form, biological uptake thing particulate is separated out for above-mentioned biological uptake thing particulate starting material solubleness the 2nd solvent also lower than the 1st solvent.

Contain medicine in the above-mentioned biological uptake thing.The present invention, available diversified medicine is implemented.Medicine is preferably the organic substance that pure in fact state exists.Medicine can disperse on low-solubility ground at least a solvent, need be solvable at least a solvent.So-called low-solubility, the meaning is meant that medicine under treatment temp (for example, room temperature), has less than about 10mg/mL in solvent (for example, water), be preferably the solvability less than about 1mg/mL.In addition, the solvable meaning here is meant that 10mg/mL dissolves abovely.What explain is, also can solvent heated or is cooled off as required.And, as required, can be with dispersion agent (tensio-active agent) or water-soluble polymer, stablizer, preservatives, pH adjusts agent, etc. imbibition agent etc., adds the 1st solvent or the 2nd solvent in advance to, or among its two side.

Suitable pharmaceutical for example, can be selected from the known drug class that comprises following medicine: anodyne, antiphlogistic drug, deinsectization medicine, anti-arrhythmia medicine; Microbiotic (comprising PCs), the solid medicine of anti-freezing, anti-depressor, antidiabetic drug, antiepileptic drug, antihistaminic; Anti-malignant-tumor agent, diet pill, appetite suppressant, depressor, anti-muscarine medicine, antimycobacterial drug; Anti-true tumor medicine (anti-true tumor medicine), immunosuppressive drug, antithyroid drug, antimicrobial drug, antiviral drug, the uneasy medicine (soporific and neuroleptic drug) of removing; Astringent, suprarenal gland disposition beta receptor blocker, Blood Preparations and substitute blood plasma, muscular degeneration of heart power medicine, contrast medium, hydrocortisone; Cough Depressant (expectorant and mucus are destroyed medicine), the diagnosis medicine, the diagnosis picture forms medicine, and hydragog(ue), Dopamine HCL are made medication (Mirapexin), styptic; Immune substance, lipid is regulated medicine, muscle relaxant, parasympathetic stimulation energizer, Parathyroid thyrocalcitonin and bisphosphonates class; Prostaglandin(PG), radioactivity medicine, sexual hormoue (comprising steroidal compounds), anti-allergy agent, energizer and appetite decline material; Adrenergic agent, thyroid drug, vasodilator and xenthophylls class, agent for treating cataract, adrenocortical hormone agent.As preferred medicine, what can enumerate in water low solubility is the medicine of purpose with oral and injection.Comprise the medicine class of putting down in writing these grades and the inventory of each grade, can be referring to " Martindale, The Extra Pharmacopoeia, the 29th edition, The Pharaceutical Press, London, 1989 ".These medicines are all by commercially available, or can be with known method manufacturing in this technical field.

As at the concrete example of implementing the useful medicine of benzene inventive aspect, enumerate as representational: 17-α-pregna-2,4-diene-20-yno-(2,3-d)-isoxazol-17-ol (danazol), tacrolimus hydrate, lutein, tranilast; Benzbromarone, vialidon, (6-methoxyl group-4-(1-methylethyl)-3-oxo-1,2-benzisothiazole-2 (3H)-yl) methyl 2,6-dichlorobenzoic acid ester 1, (WIN 63 for the 1-dioxide; 394), 3-amino-1,2,4-phentriazine-1,4-dioxide (WIN 59,075); ピ Port サ Le Off ア system, ピ Port サ Le Off ア Application, NSC 94600, PARACETAMOL BP98, Xaxa, amiodarone; Colestyramine (コ レ ス チ Off ミ Application), colestipol, Sodium Cromoglicate (Network ロ モ リ Application Na ト リ ウ system), salbutamol (ア Le Block テ ロ one Le), sucralfate (ス Network ラ Le Off エ one ト), sulfasalazine; Minoxidil, テ Application パ ゼ パ system, alprazolam, Propoxyphene, auranofin (オ one ラ ノ Off イ Application), Oxacyclotetradecane,erythromycin deriv; Ring spore mycin, acyclovir, ganciclovir, VP (エ ト Port サ イ De), TV (メ Off ア ラ Application), methotrexate (メ ト ト リ キ セ one ト); ミ ノ キ サ Application ト ロ Application, daunorubicin, Zorubicin, megestrol, tamoxifen, medroxyprogesterone; Nystatin, terbutaline, amphotericin B, Asprin, Ibuprofen BP/EP, Naproxen Base; Indomethacin, diclofenac, KP, FLURBIPROFEN USP24, diflunisal, ethyl-3; 5-diethylamide-2,4,6-phenyl triiodide manthanoate (WIN 8883), ethyl (3, two (acetylamino)-2,4 of 5-; 6-phenyl triiodide methanoyl) acetic ester (WIN 12,901) and ethyl-2-(3, two (acetylamino)-2,4 of 5-, 6-phenyl triiodide methanoyl) acetic ester (WIN 16,318).

In the optimal way of this invention; Medicine is the immunosuppressive drug as danazol (danazol) or tacrolimus hydrate, the anti-allergy agent as tranilast, the steroide as lutein; Antiviral drug, anti-malignant-tumor agent or anti-inflammatory agent.

As preferred especially stablizer dispersion agent (tensio-active agent), can enumerate X 2073, sodium lauryl sulphate; Trombovar, pentadecyl sodium sulfate, sodium octyl sulfate; Sodium oleate, sodium laurate, StNa; Calcium stearate, Tween20 and Tween80 (these can obtain, be the polyoxyethylene sorbitan fatty acid esters class from ICI Specialty Chemicals); Vinylpyrrolidone polymer, tyloxapol (tyloxapol), Pluronic F68 and F108 (this can obtain from BASF, be the segmented copolymer of oxyethane and polypropyleneoxide); Tetronic 908 (T908) (this can obtain from BASF, for from oxyethane and propylene oxide 4 functionality segmented copolymers) to the continuous affixture of quadrol; VISOSE, Yelkin TTS, dioctylis sulfosuccinas natricus (this can obtain, be the dioctyl ester of sodium sulfo-succinate from American Cyanamid); Duponol P (this can obtain, be Sodium Lauryl Sulphate BP/USP from DuPont); (this can obtain, be the alkyl aryl polyether sulphonate from Rohm and Haas to Triton X-200, Carbowax 3350 and 934 (this can obtain, be polyethylene glycols from Union Carbide), Crodesta F-110 (this can obtain from Croda Inc., be the mixture of sucrose stearate and sucrose distearate); Crodesta 5L-40 (this can obtain from Croda Inc.), (this is C to reach SA90HCO ₁₈H ₃₇CH ₂(CON (CH ₃) CH ₂(CHOH) ₄CH ₂OH) ₂), in addition, benzethonium chloride, the quaternary ammonium tensio-active agent of benzalkonium chloride etc. or polyethylene oxide higher alcohols ethers; The glycerol fatty acid ester class, polyethylene oxide solidifies Viscotrol C, polyoxyethylene fatty acid ester, T 46155 nonylplenyl ether; Polyoxyethylene octyl phenyl ether, sorbitan fatty acid esters, propylene glycol fatty acid ester; Fatty acid polyglycol terepthaloyl moietie, polyglycerol fatty acid ester, the nonionic surfactant class of sucrose fatty ester etc.Can separately use according to the biological uptake thing particulate and the evolution reaction of purpose.

As water-soluble polymer, can enumerate methylcellulose gum, TKK 021, propyl methocel, propyl cellulose, carboxy methyl cellulose, Z 150PH, Vinylpyrrolidone polymer etc.

This content of medicines among the present invention is not done special restriction.Can make the suspension-s of high density, also can meet working concentration and dilute and process preparation.

As stablizer, can enumerate sodium ethylene diamine tetracetate, S-WAT, sodium sulfite anhy 96, Sulfothiorine, butylated hydroxytoluene, Viteolin etc.

As preservatives, can enumerate p-Hydroxybenzoate, butylene-chlorohydrin, phenylethyl alcohol, benzalkonium chloride, benzethonium chloride, glyconic acid chlorhexidine, alkyl polyamino ethyl glycine class, Sorbic Acid etc.

As pH adjustment agent, can enumerate hydrochloric acid, sulfuric acid, acetate, lactic acid, Hydrocerol A, tartrate, oxysuccinic acid, phosphoric acid, boric acid, sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, monoethanolamine, diethylolamine, DIETHANOL AMINE, ammonia and these salt etc.

As etc. the imbibition agent, can enumerate sodium-chlor, Repone K, calcium chloride, N.F,USP MANNITOL etc.

As the solvent that in the fluid that contains at least a above-mentioned biological uptake thing particulate starting material, uses among the present invention; Can select the water of ultrapure water or ion exchanged water etc. aptly and according to purpose such as methyl alcohol, ethanol, acetone, N (DMF, N,N-DIMETHYLACETAMIDE according to purpose; The water Combination organic solvent that DMSO 99.8MIN. (DMSO) is such, the water as octane, hexanaphthene, benzene, YLENE, diethyl agent ether, ETHYLE ACETATE so not Combination organic solvent is implemented.

What explain is; Biological uptake thing particulate of the present invention; As long as its biological uptake is as purpose, it is not done special the qualification, can enumerate and for example as the medicine in the pharmaceuticals, absorb in vivo, appear in vivo that effect is the material of purpose; As as the permanent white of contrast medium, through intravital material; Material is used in transmission like the pharmaceutical cpd in the drug delivery system, perhaps, and the midbody of material that as makeup, on biological skin, is coated with and food and above-mentioned substance etc.

The evolution reaction of particulate, Fig. 1 (A) shown device, can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, between 2, on one side one side uniform mixing takes place by the strong hand.

At first; From the 1st d1 of importing portion as 1 stream; With the above-mentioned solution that contains the 1st solvent, importing can be near each other the subtend configuration, that at least one side is rotated with respect to the opposing party processing discretely with 1,2 in face, the film fluid that generation is made up of the 1st fluid between this processing is with face.

Then,, can form the solution of solubleness 2nd solvent also lower, directly import the above-mentioned film fluid that constitutes by the 1st fluid than the 1st solvent from the 2nd d2 of importing portion as other stream.

As stated; Through fluidic supply pressure and the processing that is being rotated with face between applied pressure pressure equilibrium and with fixed distance processing with face 1, between 2; The solution and the 2nd solvent that contain the 1st solvent mix, and can carry out the evolution reaction of particulate.

What explain is, owing to can carry out above-mentioned reaction with face 1, between 2 and get final product handling, therefore, also can import the 2nd fluid from the 1st d1 of importing portion on the contrary with above-mentioned, imports the 1st fluid from the 2nd d2 of importing portion.That is, the appellation of the what is called the 1st, the 2nd in each solvent is the n of the solvent of a plurality of existence of expression, and just also can there be the solvent more than the 3rd in the mark in order to discern.

As stated, remove the 1st d1 of importing portion, beyond the 2nd d2 of importing portion; The 3rd d3 of importing portion also can be set on treatment unit, under this situation, for example can be from each importing portion; To contain solution, the 2nd solvent of the 1st solvent, the solution that contains the stablizer dispersion agent imports in the treatment unit respectively.Like this, but each the management each solution concentration, pressure, can more critically control evolution reaction.Even under the situation that is provided with the importing portion more than the 4th, the fluid sectionalization that equally also can be so will import to treatment unit.

Secondly, describe for changing the method that biological uptake thing particulate is separated out through neutralization reaction or pH.Following method feature is; Be in the fluid to change when biological uptake thing particulate starting material being separated out make biological uptake thing particulate through neutralization reaction or pH; With above-mentioned fluid as can in this film fluid, biological uptake thing particulate being separated out near the mutual film fluid that forms between with face of subtend processing that set, that at least one side is rotated with respect to the opposing party discretely through neutralization reaction or pH variation.

Below, as concrete example of the present invention, with absorb in the organism as contrast medium, permanent white biological uptake thing particulate is that example describes more in detail.But the present invention is bound to this instance.

This reaction, Fig. 1 (A) shown device, can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, between 2, on one side one side uniform mixing takes place by the strong hand.

At first; From the 1st d1 of importing portion as 1 stream; Will as the 1st fluidic contain at least a bariumchloride, hydrated barta in addition, the fluid of the solution of the water soluble barium salt of NSC 75794 etc.; Importing can be near each other the subtend configuration, that at least one side is rotated with respect to the opposing party processing discretely with 1,2 in face, the film fluid that generation is made up of the 1st fluid between this processing is with face.

Then,, will contain the fluid in the water-soluble sulfate solution of at least a sulfuric acid, ammonium sulfate etc., directly import the above-mentioned film fluid that constitutes by the 1st fluid as the 2nd fluidic from the 2nd d2 of importing portion as other stream.

As stated, through fluidic supply pressure and the processing that is being rotated with face between applied pressure pressure equilibrium and with fixed distance processing with face 1, between 2, the 1st fluid and the 2nd fluid interflow in the film fluid.The 1st fluid and the 2nd fluid are mixed in this film fluid, make above-mentioned 2 kinds of substance reactions.More specifically, change, can carry out the reaction that permanent white organism picked-up thing particulate generates through neutralization reaction or pH.

Secondly, the situation of the method that obtains the biological uptake thing particulate beyond the permanent white is described.

Here, relevant with separating out of above-mentioned illustrative permanent white simple chemical reaction formula (ionic reaction formula) is following form.

(ionic reaction formula)

Ba ²⁺+SO ₄ ^2-→BaSO ₄

Neutralization reaction among the present invention comprises the neutralization reaction as general the most basic said acid-base reaction, that is, two sides' character is cancelled out each other in the neutralization reaction that generates water and salt simultaneously and the above-mentioned ionic reaction formula as the cationic material in the soda acid ²⁺With SO as the anionic property material ₄ ^2-React and generate BaSO ₄The reaction of such material.And the definition of the bronsted lowry acids and bases bronsted lowry under this situation can be the definition of Arrhenius, also can be the definition in bronsted-Lao, also can be Louis's definition.

Here, through changing used cationic material or anionic property material, can change the material of purpose and obtain.Cationic material or anionic property material are not done special qualification, can be like Na ⁺And Cl ^-Monatomic ion so also can be the polyatomic ion as NH4+ and CH3COO-, and, also can be complexing ion.In addition, particularly as in the pharmaceutical medicine etc. in large quantities the part of structure that can see, in organism in the effects of ion change also can implement.

What explain is also can contain same ion among the 1st fluid and the 2nd fluidic two sides.

In addition, when carrying out above-mentioned neutralization reaction, also can follow the variation of the pH of solvent.

Particle diameter, single dispersity of the biological uptake thing particulate that obtains with the present invention; Or the control of crystal type; Can be through change handling with the rotating speed of face 1,2 or processing with face 1, distance and film flow rate of fluid or temperature between 2, perhaps material concentration etc. is regulated.

The biological uptake thing particulate that the present invention obtains forms desirable size-grade distribution/size distribution, and the crystallization degree is that benchmark is more than 50% with the total quality of this particle of obtaining.And contain the liquid of this particle, coagulation sedimentation or particles aggregate are not stable dispersion-s through not showing for a long time after its modulation yet.In addition,, therefore can control particle diameter, be rotated with respect to the opposing party through at least one side who handles with face because the processing that subtend sets can freely be adjusted with the interval of face, can free crystallization control shape.

In addition, the dispersion-s that this invention obtains is stable, and this dispersion-s is made up of liquid dispersion medium and above-mentioned biological uptake thing particulate.And, in containing biological uptake thing particulate of the present invention or this dispersion of particles body, mix pharmaceutically permissible carrier, can obtain medical composition.

What explain is, shown in following embodiment, and under the situation that this dispersion-s is used as suspension eye droppings soup, because of the rerum natura of medicine, not being dissolved as prerequisite, but preferred pH 3～9, more preferably pH 3.0～6.5.In the scope in addition, because stimulating eyes is become big, therefore not preferred.

Above-mentioned 90% particle diameter biological uptake thing particulate, size-grade distribution/size distribution that obtains be preferably 500nm (that is, show particle diameter greater than the particle of 500nm in all particles proportion less than 10%) below.Through 90% particle diameter that makes size-grade distribution/size distribution is below the 500nm, has prevented that oversize particle from forming nuclear, carrying out the agglutinative phenomenon, and surface-area increases, and apparent solubility improves, and therefore the cornea perviousness of the effective constituent in suspension eye droppings soup improves.

The viewpoint of filtration sterilization is preferably below the 220nm through put drops in one's eyes 90% particle diameter of size-grade distribution/size distribution of liquor of suspension, makes filtration sterilization become possibility, can carry out than the asepticize cheaply of technology in the past.

The filtration sterilization strainer as long as it is the commercially available aseptic strainer of assurance, can use the strainer of various materials.As material, for example can enumerate rhodia, polycarbonate, PVDF (PVDF) etc.

The size of the pore of strainer is preferably used below the 0.45 μ m, more preferably below the 0.22 μ m.Under situation greater than the size-grade distribution/size distribution of above-mentioned scope, can cause that the mesh of filter for filtration stops up, yield reduces, and is therefore not preferred.

Suspension eyedrop among the present invention adds tensio-active agent and/or water-soluble polymer, is the scope of 20mV～150mV with the absolute value of the Zero Energy Thermonuclear Assembly (Zeta) current potential of this drug particle, can form dispersion stabilization well thus.The amount of used tensio-active agent water-soluble polymer in the adjustment of Zero Energy Thermonuclear Assembly (Zeta) current potential because of pH is different, but is preferably 0.05%～3% scope in the suspension eyedrop.

Like this, can make that to be dispersed with average primary particle diameter be 0.5～10000nm, preferred 1～500nm, the more preferably aqueous dispersion (suspension-s) of the biological uptake thing particulate of 30～200nm.And; In the solution that contains biological uptake thing particulate starting material, added under the situation of above-mentioned dispersion agent; Can make be dispersed with dispersion agent from the teeth outwards by coordination the aqueous dispersion (suspension-s) of biological uptake thing particulate, the redispersibility of the biological uptake thing particulate that obtains becomes very good.In addition; Pollutent is few in manufacturing process; Therefore can highly control its crystallization degree under the situation that crystallization is separated out, obtain under the situation of biological uptake thing particulate that biological uptake as pharmaceuticals, makeup is a purpose, it is method of manufacture especially easily.

What explain is, " particle diameter " that use in this specification sheets be meant, be utilized in the known common particle size determination method in present technique field, for example, and dynamic light scattering method laser diffraction mode etc. and the volume average particle size measured.

Disposing the level of the effective level of medicament, is the significant quantity of replying for the desirable treatment of the specific combined thing of administration and method in order to obtain.Therefore, selected consumption level relies on certain drugs, desirable result of treatment, administration path, desirable disposal time length and other factor.As put down in writing, the medical composition of this invention demonstrates the surprising high organism internal absorption factor as specifying among the following embodiment, is highly profitable.

The medical composition of this invention is thought oral and be particularly useful in the non-oral administration method of representative with the intravenous injection.In the past can not intravenous difficult water soluble drug, also can expect to carry out administration safely through the present invention.And medicine that can not per os owing to lack the organism utilising efficiency also can be through the present invention's administration effectively.

Below, explain in further detail that for disclosed embodiment of the present invention still, the present invention is defined in these embodiment.

What explain is; In following embodiment; So-called " from central authorities "; Refer to such an extent that be the meaning of " from the 1st d1 of importing portion " of treatment unit shown in above-mentioned, Fig. 1 (A), the 1st fluid is meant that the above-mentioned the 1st is processed liquid, that the 2nd fluid is meant is above-mentioned, treatment unit shown in Fig. 1 (A) " that import from the 2nd d2 of importing portion, above-mentioned the 2nd is processed liquid.

The manufacturing of (embodiment D1) danazol particle

Shown in Fig. 1 (A); What use had that subtend sets can be near isolating processing with face, in the film fluid of processing with face 1, formation between 2 that at least one side is rotated with respect to the opposing party, spread the reaction unit that mixes equably; With the aqueous solution that is dissolved with medicine with to the low solution of this drug solubility and the mixed solution of macromolecule dispersing agent or stablizer, in the film fluid, mix and carry out partial crystallization and react.

Will be from central authorities as the 1st fluidic 0.1%Tween80 aqueous solution; To supply with pressure/back pressure=0.02MPa/0.01Mpa, rotating speed 1000rpm, 35 ℃ of liquor chargings of liquor charging temperature; To use dissolve with ethanol the liquid of powder danazol as the 2nd fluid, import with 10ml/min and to handle with between face.The 1st fluid and the 2nd fluid are mixed in the film fluid, and the danazol dispersion soln is discharged from face from handling with 30g/min.

With the danazol dispersion soln that reclaims; Use is measured as the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of measuring principle with dynamic light scattering method; Volume average particle size is 65nm as a result, and the CV value of its size-grade distribution/size distribution is 17%.In addition; In the danazol dispersion soln that reclaims, adding ethanol dissolves; Utilize alpha counter (リ オ Application (strain) system; Trade(brand)name: alpha counter KS65) impurity is sneaked into confirm, the above particle of 10 μ m has 13 among the 1ml as a result, and the above particle of 25 μ m has 1 (0.05% danazol solution).

Secondly, the danazol dispersion soln that reclaims is dry, utilize X-ray diffraction differential scanning calorimeter DSC and FFIR photometer FT-IR to carry out the evaluation of material, the result is consistent with danazol based powders (former end), obtains crystallization degree 80%.

Giving the biological utilization ratio (BA) under the situation of dog administration with the invention described above particulate (volume average particle size 65nm) as nano suspending liquid is 92.9%.By with commercially available article (volume average particle size: be 5.1% 10 μ m) as the biological utilization ratio (BA) under the situation of suspension-s administration.This we can say that the organism internal absorption factor rises significantly.

The desired energy fluence of micronize is compared with the pulverizing that the kibbler SS5-100 of applicant's manufacturing of using the application is carried out, and is 1/32000th.

Secondly; The change condition; Will be from central authorities as the 1st fluidic 0.1%Tween80 aqueous solution; To supply with pressure/back pressure=0.10MPa/0.02Mpa, rotating speed 1000rpm, 35 ℃ of liquor chargings of liquor charging temperature, will use dissolve with ethanol the liquid of powder danazol as the 2nd fluid, import with 10ml/min and to handle with between face.The 1st fluid and the 2nd fluid are mixed in the film fluid, and the danazol dispersion soln is discharged from face from handling with 70g/min.

With the danazol dispersion soln that reclaims; Use is measured as the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of measuring principle with dynamic light scattering method; Volume average particle size is 135nm as a result, and the CV value of its size-grade distribution/size distribution is 19%.

Secondly, the danazol dispersion soln that reclaims is dry, utilize X-ray diffraction differential scanning calorimeter DSC and FFIR photometer FT-IR to carry out the evaluation of material, the result is consistent with the danazol based powders, obtains crystallization degree 75%.

Change condition again; Will be from central authorities as the 1st fluidic water; To supply with pressure/back pressure=0.02MPa/0.01Mpa, rotating speed 1000rpm, 35 ℃ of liquor chargings of liquor charging temperature; To use liquid that the Tween80 mixed ethanol dissolved the powder danazol as the 2nd fluid, and import with 10ml/min and handle with between face.The 1st fluid and the 2nd fluid are mixed in the film fluid, and the danazol dispersion soln is discharged from face from handling with 30g/min.

With the danazol dispersion soln that reclaims; Use is measured as the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of measuring principle with dynamic light scattering method; Volume average particle size is 78nm as a result, and the CV value of its size-grade distribution/size distribution is 18%.

Secondly, the danazol dispersion soln that reclaims is dry, utilize X-ray diffraction differential scanning calorimeter DSC and FFIR photometer FT-IR to carry out the evaluation of material, the result is consistent with the danazol based powders, obtains crystallization degree 82%.

The manufacturing of (embodiment D2) tacrolimus hydrate particles

Will be from central authorities as the 1st fluidic 0.1%Tween80 aqueous solution; To supply with pressure/back pressure=0.02MPa/0.01Mpa, rotating speed 2000rpm, 30 ℃ of liquor chargings of liquor charging temperature; To use dissolve with ethanol the liquid of tacrolimus hydrate as the 2nd fluid, import with 10ml/min and to handle with between face.The 1st fluid and the 2nd fluid are mixed in the film fluid, and tacrolimus hydrate dispersion soln is discharged from face from handling with 30g/min.

With the tacrolimus hydrate dispersion soln that reclaims; Use is measured as the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of measuring principle with dynamic light scattering method; Volume average particle size is 116nm as a result, and the CV value of its size-grade distribution/size distribution is 16%.

Secondly; The tacrolimus hydrate dispersion soln that reclaims is dry; Utilize X-ray diffraction differential scanning calorimeter DSC and FFIR photometer FT-IR to carry out the evaluation of material, the result is consistent with tacrolimus hydrate based powders, obtains crystallization degree 90%.

Next change condition; Will be from central authorities as the 1st fluidic 0.1%Tween80 aqueous solution; To supply with pressure/back pressure=0.02MPa/0.01Mpa, rotating speed 1000rpm, 30 ℃ of liquor chargings of liquor charging temperature; To use dissolve with ethanol the liquid of tacrolimus hydrate as the 2nd fluid, import with 10ml/min and to handle with between face.The 1st fluid and the 2nd fluid are mixed in the film fluid, and tacrolimus hydrate dispersion soln is discharged from face from handling with 20g/min.

With the tacrolimus hydrate dispersion soln that reclaims; Use is measured as the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of measuring principle with dynamic light scattering method; Volume average particle size is 98nm as a result, and the CV value of its size-grade distribution/size distribution is 13%.

Secondly; The tacrolimus hydrate dispersion soln that reclaims is dry; Utilize X-ray diffraction differential scanning calorimeter DSC and FFIR photometer FT-IR to carry out the evaluation of material, the result is consistent with tacrolimus hydrate based powders, obtains crystallization degree 95%.

The manufacturing of (embodiment D3) tranilast particle

Will be from central authorities as the 1st fluidic water; To supply with pressure/back pressure=0.02MPa/0.01Mpa, rotating speed 1000rpm, 27 ℃ of liquor chargings of liquor charging temperature; The liquid that in the potassium hydroxide solution of the pH value 13 of having added Tween80, has dissolved tranilast as the 2nd fluid, is imported processing with between face with 10ml/min.The 1st fluid and the 2nd fluid are mixed in the film fluid, and the tranilast dispersion soln is discharged from face from handling with 30g/min.

With the tranilast hydrate dispersion soln that reclaims; Use is measured as the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of measuring principle with dynamic light scattering method; Volume average particle size is 120nm as a result, and the CV value of its size-grade distribution/size distribution is 15%.

Secondly; The tranilast dispersion soln that reclaims is used the Mierocrystalline cellulose dialysis tubing, dialyse, except that after desalting with pure water; Dry; Utilize X-ray diffraction differential scanning calorimeter DSC and FFIR photometer FT-IR to carry out the evaluation of material, the result is consistent with the tranilast based powders, obtains crystallization degree 86%.

(volume average particle size 120nm) processes the O/W paste formulation with the invention described above particulate, and use-testing skin (LSE-high) carries out 8 hours skin perviousness test, and the result illustrates with based powders (volume average particle size 45 μ m) and compares 5 times perviousness.

(embodiment D4～D7) the permanent white particle separates out

Shown in Fig. 1 (A); Use have that subtend sets can near isolating processing with face, in processing that at least one side is rotated with respect to the opposing party with face 1, between 2 in the formed film fluid, spread the reaction unit that mixes equably; Make barium chloride solution and aqueous sodium persulfate solution in the film fluid, neutralization reaction take place, carry out separating out of permanent white.

(embodiment D4)

To supply with pressure/back pressure=0.02MPa/0.01Mpa, rotating speed 500rpm, 25 ℃ of liquor chargings of liquor charging temperature, 17% barium chloride solution as the 2nd fluid, be imported processing with between face with 10ml/min as the 1st fluidic 25% aqueous sodium persulfate solution from central authorities.The 1st fluid and the 2nd fluid are mixed in the film fluid, and the permanent white dispersion soln is discharged from face from handling with 20ml/min.

Secondly, from this dispersion liquid, remove impurity,, observed the permanent white particulate in this dispersion liquid with transmission electron microscope (TEM) with dialysis tubing.From wherein choosing 100 particles arbitrarily, measure average primary particle diameter, the result is 50nm.

And; The Powdered permanent white particulate that this permanent white dispersion liquid vacuum lyophilization is obtained drops in the ion exchanged water once more, stirs with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system); The result obtains the permanent white particle dispersion liquid once more; Identical before particle diameter and the vacuum lyophilization, average primary particle diameter is 50nm, and the redispersibility of the permanent white particulate powder of confirming to obtain is good.

For embodiment D5～D7, use aqueous sodium persulfate solution and the barium chloride solution identical with embodiment D1, change rotating speed, supply pressure, back pressure obtains permanent white particle dispersion and permanent white powder.

(Comparative Example D 1)

Use ClearMix (M technology society system) to stir above-mentioned aqueous sodium persulfate solution on one side, form the permanent white particle dispersion liquid Yi Bian add above-mentioned barium chloride solution.At this moment, ClearMix has carried out 30 minutes stirring with rotating speed 20000rpm.Obtain the permanent white particle dispersion liquid of average primary particle diameter 900nm.In addition, likewise confirm as redispersibility, but particle diameter is 1700nm behind the redispersion, and compares strong aggegation before the vacuum lyophilization with embodiment.The above results is shown in table 3.What explain is that embodiment 4～7 in the table and comparative example 1 are represented the foregoing description D4～D7 and Comparative Example D 1 respectively.

[table 3]

(embodiment D8～D10) the manufacturing of fluorometholone suspension eyedrop

To with rotating speed 100～1000rpm, 25 ℃ of liquor chargings of liquor charging temperature, the liquid that has dissolved fluorometholone in the pyridine be imported processing with between face as the 2nd fluid as the 1st fluidic 0.05%Tween80 solution from central authorities.The 1st fluid and the 2nd fluid are mixed in the film fluid, and fluorometholone suspension-s is discharged from face from handling.With the fluorometholone suspension-s that reclaims, use with dynamic light scattering method and measure as the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of measuring principle.The fluorometholone suspension-s of dried recovered utilizes X-ray diffraction differential scanning calorimeter DSC and FFIR photometer FT-IR to carry out the evaluation of material, and the result is consistent with the fluorometholone based powders.

In addition, Comparative Example D 2 and D3, ((M technology society system ClearMix2.2S), has been carried out 30min preparation grinding dispersion with rotating speed 20000rpm with the fluorometholone based powders to use homogenizer.(M technology society system SS5-100), has been carried out micronize processing, grinding dispersion to Comparative Example D 2 after this further using ultra-thin membrane type high speed rotating kibbler.For Comparative Example D 4, do not carry out arbitrary processing, only carried out the pH adjustment of based powders.And, make the suspension-s that is dispersed with the based powders of having carried out above-mentioned processing.Above-mentioned treatment condition and size-grade distribution/particle size distribution measuring result is shown in table 4.What explain is that embodiment 8～10 in the table and comparative example 2～4 are represented the foregoing description D8～D10 and Comparative Example D 2～D4 (table 5～10 are like this too) respectively.

[table 4]

< the adaptive affirmation of filtration sterilization >

For the foregoing description D8～D10, and each experimental liquid of six examples of Comparative Example D 2～D4, use the PVDF strainer of pore with 0.22 μ m, carried out the filtration sterilization processing.With the fluorometholone concentration before and after the HPLC mensuration filtration sterilization, the yield when obtaining the filtration sterilization processing.The result is shown in table 5.

[table 5]

	Embodiment 8	Embodiment 9	Embodiment 10	Comparative example 2	Comparative example 3	Comparative example 4
							Concentration [%] before filtering	0.0050	0.0052	0.0050	0.0051	0.0050	0.0051
Filter back concentration [%]	0.0012	0.0046	0.0050	Can not filter	Can not filter	Can not filter
							Yield [%]	24.0	88.5	100.0	-	-	-

In addition, the yield that has under the situation of PVDF strainer of 0.45 μ m pore in use is shown in table 6.

[table 6]

	Embodiment 8	Embodiment 9	Embodiment 10	Comparative example 2	Comparative example 3	Comparative example 4
							Concentration [%] before filtering	0.0049	0.0052	0.0051	0.0051	0.0050	0.0051
Filter back concentration [%]	0.0040	0.0052	0.0051	Can not filter	Can not filter	Can not filter
							Yield [%]	81.6	100.0	100.0	-	-	-

Secondly; To dissolve the liquid (solvent is an acetone) of fluorometholone as the 1st fluidic 0.05%Tween80 solution with as the 2nd fluidic; After the strainer sterile filtration with 0.22 μ m, again with rotating speed 100rpm, the 1st fluid and the 2nd fluidic ratio of mixture 4: 1; During delivery flow 150ml/min, obtain the particle of volume average particle size 2.2 μ m.As comparative example, behind the based powders dry sterilization, use homogenizer (M technology society system; ClearMix2.2S:18000rpm; 30min) and ultra-thin membrane type high speed rotating kibbler (M technology society system SS5-100) has been carried out the powder that micronize is handled, and volume average particle size is 2.1 μ m.And the desired energy amount of casting in the enforcement of the method that the present invention relates to is compared with above-mentioned comparative example, is about about 1/30000th.

(embodiment D11～D13) the manufacturing of pirenoxine suspension eyedrop

Will be from central authorities as the aqueous nitric acid of the 1st fluidic 0.05mol/L, with rotating speed 100～1000rpm, 25 ℃ of liquor chargings of liquor charging temperature, the liquid that has dissolved pirenoxine in the sodium hydroxide with 0.1mol/L imports as the 2nd fluid to be handled with between face.The 1st fluid and the 2nd fluid are mixed in the film fluid, and pirenoxine suspension-s is discharged from face from handling.The pirenoxine suspension-s that reclaims is dialysed with pure water with dialysis tubing, remove by product thus, use with the particle size distribution device (trade(brand)name of day machine dress strain (strain) system: microtrac UPA150) measure of dynamic light scattering method as measuring principle.The pirenoxine suspension-s of dried recovered utilizes X-ray diffraction differential scanning calorimeter DSC and FFIR photometer FT-IR to carry out the evaluation of material, and the result is consistent with the pirenoxine based powders.

On the other hand, Comparative Example D 5 and D6, (M technology society system ClearMix2.2S), has been carried out 30min preparation grinding dispersion with rotating speed 18000rpm with the pirenoxine based powders to use homogenizer.(M technology society system SS5-100), has been carried out micronize processing, grinding dispersion to Comparative Example D 5 after this further using ultra-thin membrane type high speed rotating kibbler.Do not carry out arbitrary processing for Comparative Example D 7, only carried out the pH adjustment of based powders.And, make being dispersed with the suspension-s that has carried out above-mentioned processing based powders.

Above-mentioned treatment condition and size-grade distribution/particle size distribution measuring result is shown in table 7.

[table 7]

Desired energy in the micronize, (M technology society system SS5-100) is compared, and is 1/1/3.2nd * 107～3.2 * 104th, and energy efficiency is excellent with ultra-thin membrane type high speed rotating kibbler.

And, for embodiment D11～D13, pH being adjusted under 3.0～5.5 the situation, median size is 8nm～98nm, 90% particle diameter is 89nm～186nm.

< light stability test >

With the foregoing description D11～D13, and each experimental liquid of Comparative Example D 5～D7, every 10mL glass transparent bottle of packing into utilizes the light source irradiation light of rayed trier by 2000Luxhr.To the experimental liquid of each bottle through the time sample, measure pirenoxine concentration with HPLC, the remaining ratio (%) of assessment pirenoxine.The result is shown in table 8.What explain is, the numerical value in the table is the MV of experiment number (N) 3 times.

[table 8]

The MV of N=3

< test of skin perviousness >

In horizontal 2 Room diffusion units (useful area 0.3cm2, unit volume 5mL, 32 ℃ of temperature), the cornea of the man rabbit extraction of Japan is fixed so that corneal epithelium becomes donor side.Storing solution (reserve liquid) is the imbibition damping fluids such as phosphoric acid of pH7.5.In donor side, use each experimental liquid of embodiment D11～13 and Comparative Example D 5～Comparative Example D 7 respectively.The moment to add each testing liquid in donor side is the zero-time scale, through the time ground storing solution is sampled.Measure the pirenoxine concentration in the test liquid with HPLC, estimate the pirenoxine amount that has moved cornea.The result is shown in table 9.What explain is, the numerical value in the table is the MV of experiment number (N) 3 times.

[table 9]

Unit [ng/mL].Wherein, the MV of expression N=3

< the adaptive affirmation of filtration sterilization >

For the foregoing description D11～D13, and each experimental liquid of six examples of Comparative Example D 5～D7, use has the PVDF strainer of the pore of 0.22 μ m, carries out filtration sterilization and handles.With the pirenoxine concentration before and after the HPLC mensuration filtration sterilization, the yield when obtaining the filtration sterilization processing.The result is shown in table 8.

[table 10]

	Embodiment 11	Embodiment 12	Embodiment 13	Comparative example 5	Comparative example 6	Comparative example 7
							Concentration [%] before filtering	0.0050	0.0052	0.0049	0.0052	0.0050	0.0051
Filter back concentration [%]	0.0049	0.0052	0.0049	0.0051	0.0012	Can not filter
							Yield [%]	98.0	100.0	100.0	98.1	24.0	-

(E) ceramic nanoparticle

Below, the reaction that ceramic nanoparticle of the present invention is generated describes.

This reaction, as Fig. 1 (A) shown device, can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, between 2, and meanwhile by the strong hand uniform mixing take place.

At first; From the 1st d1 of importing portion as 1 stream; The fluid that will contain pH adjustment agent as the 1st fluidic; Importing can be near each other the subtend configuration, that at least one side is rotated with respect to the opposing party processing discretely with 1,2 in face, the film fluid that generation is made up of the 1st fluid between this processing is with face.

Then, the 2nd d2 of importing portion from as other stream will contain the fluid that reactant is a Ceramic Material as the 2nd fluidic, directly import the above-mentioned film fluid that is made up of the 1st fluid.

As stated; The pressure equilibrium of applied pressure between the processing of supply with pressing and being rotated through fluidic is with face and with fixed distance processing with face 1, between 2; The 1st fluid and the 2nd fluid are mixed, and Ceramic Material is hydrolyzed, and can generate the reaction of ceramic nanoparticle.

What explain is, owing to can carry out above-mentioned reaction with face 1, between 2 and get final product handling, therefore, also can import the 2nd fluid from the 1st d1 of importing portion on the contrary with above-mentioned, imports the 1st fluid from the 2nd d2 of importing portion.That is, the appellation of the what is called the 1st, the 2nd in each solvent is the n of the solvent of a plurality of existence of expression, and just also can there be the solvent more than the 3rd in the mark in order to discern.

The particle diameter of the ceramic nanoparticle that obtains, single dispersity, or the control of crystal type can be through change handling with the rotating speed of face 1,2 or processing with face 1, distance and film flow rate of fluid or temperature between 2, and perhaps material concentration etc. is regulated.

Utilizing the CV value in the size-grade distribution of the ceramic nanoparticle that the present invention obtains is 5～40%, is preferably 10～20%.

With the ceramic nanoparticle that the method for manufacture of ceramic nanoparticle of the present invention obtains, do not do special qualification, for example can enumerate by aluminum oxide zirconium white, the ceramic nanoparticle that barium titanate constitutes.Pottery as other can be zeolite, cerium oxide etc.

The used Ceramic Material of the method for manufacture of ceramic nanoparticle of the present invention does not have special qualification, for example can use to be selected from Al Ba, Mg, Ca, La, Fe, Si; Ti, Zr, Pb, Sn, Zn, Cd, As, Ga; Sr, Bi, Ta, Se, Te, Hf, Mg, Ni; Mn, Co, S, Ge, Li, B, the alcoholate of at least a kind of metal of Ce, or metal-salt.

If for example be the raw material of aluminium oxide nano particle, can use aluminum alcoholate or aluminum nitrate as aluminum isopropylate, the aluminium salt as aluminum acetate, the alkali aluminate as sodium aluminate etc.

As the solvent of solution ceramic raw material, or be used to make the solvent of pH adjustment agent, do not do special qualification; Deionization exchanged water or RO water; The water of ultrapure water etc. and methyl alcohol or ethanol, beyond the alcohol of Virahol (IPA) etc., but the organic solvent of illustration toluene or YLENE etc.

In addition, among the present invention and Ceramic Material blended Ceramic Material do not do not to be defined especially, can use Mg (OR) ₂, Ca (OR) ₂, La (OR) ₃, Fe (OR) ₂, Si (OR) ₄, Ti (OR) ₄, Zr (OR) ₄In addition such metal alcoholate of (R representes alkyl) etc., also can use Ce (NO ₃) ₃And In (NO ₃) ₃Such metal-salt etc.

In addition, be used to control the pH adjustment agent of pH among the present invention during the hydrolysis Ceramic Material, do not do special qualification.Under the tart situation, can use hydrochloric acid, nitric acid, the mineral acid of sulfuric acid etc., and Hydrocerol A, the organic acid of acetate etc. etc.Under the situation of alkalescence, can use sodium hydroxide or Pottasium Hydroxide or ammonia soln etc.According to circumstances, can above-mentioned illustrative pH adjustment agent be diluted or dissolve with above-mentioned solvent and use.

As stated, remove the 1st d1 of importing portion, beyond the 2nd d2 of importing portion, the 3rd d3 of importing portion can be set on treatment unit also, under this situation, for example can pH be adjusted agent from each importing portion, the solution of Ceramic Material, the modulator of hydrolysis rate imports in the treatment unit respectively.Like this, but each manages concentration, the pressure of each solution, can more critically control the reaction that ceramic nanoparticle generates.Even under the situation that is provided with the importing portion more than the 4th, the fluid sectionalization that equally also can be so will import to treatment unit.

Below, describe in more detail for disclosed embodiment of the present invention.But the present invention has more than and is defined in these embodiment.

What explain is; In following embodiment; So-called " from central authorities "; Refer to such an extent that be the meaning of " from the 1st d1 of importing portion " of treatment unit shown in above-mentioned, Fig. 1 (A), the 1st fluid is meant that the above-mentioned the 1st is processed liquid, that the 2nd fluid is meant is above-mentioned, treatment unit shown in Fig. 1 (A) " that import from the 2nd d2 of importing portion, above-mentioned the 2nd is processed liquid.

(embodiment E 1)

Use shown in Fig. 1 (A) can be near the reaction unit that each other evenly mixes in the film fluid of subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, formation between 2 discretely; The aqueous solution that will be adjusted to pH2 with aqueous hydrochloric acid in the film fluid with the IPA solution water interflow of containing Ceramic Material, on one side the uniform mixing reaction that is hydrolyzed on one side.

To be adjusted to the aqueous solution of pH2 as the 1st fluidic with aqueous hydrochloric acid from central authorities; To supply with pressure/back pressure=0.30MPa/0.01Mpa, rotating speed 1000rpm liquor charging; To import processing with face 1, between 2 with 10ml/min as the 2nd fluidic 4% aluminum isopropylate/IPA solution.The aluminium oxide nano particle dispersion is discharged from face from handling.

Use has been used the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of laser Doppler method and has been measured size-grade distribution, and volume average particle size is 11nm as a result, and the CV value of its size-grade distribution is 18%.

(embodiment E 2)

To be adjusted to the aqueous solution of pH2 as the 1st fluidic with aqueous hydrochloric acid from central authorities; To supply with pressure/back pressure=0.10MPa/0.01Mpa, rotating speed 1000rpm liquor charging; To import processing with face 1, between 2 with 10ml/min as the 2nd fluidic 4% aluminum isopropylate/IPA solution.The aluminium oxide nano particle dispersion is discharged from face from handling.

Use has been used the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of laser Doppler method and has been measured size-grade distribution, and volume average particle size is 10nm as a result, and the CV value of its size-grade distribution is 17%.

(embodiment E 3)

To be adjusted to the aqueous solution of pH2 on one side as the 1st fluidic with aqueous hydrochloric acid from central authorities; To supply with pressure/back pressure=0.30MPa/0.01Mpa, rotating speed 2000rpm liquor charging; To import processing with face 1, between 2 with 10ml/min as the 2nd fluidic 4% aluminum isopropylate/IPA solution on one side.The aluminium oxide nano particle dispersion is discharged from face from handling.

Use has been used the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of laser Doppler method and has been measured size-grade distribution, and volume average particle size is 14nm as a result, and the CV value of its size-grade distribution is 15%.

(embodiment E 4)

To be adjusted to the aqueous solution of pH2 on one side as the 1st fluidic with aqueous hydrochloric acid from central authorities; To supply with pressure/back pressure=0.30MPa/0.01Mpa, rotating speed 1000rpm liquor charging; To import processing with face 1, between 2 with 10ml/min as the 2nd fluidic 10% aluminum isopropylate/IPA solution on one side.The aluminium oxide nano particle dispersion is discharged from face from handling.

Use has been used the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of laser Doppler method and has been measured size-grade distribution, and volume average particle size is 11nm as a result, and the CV value of its size-grade distribution is 19%.

(Comparative Example E 1)

To be adjusted to the aqueous solution 20g of pH2 on one side with aqueous hydrochloric acid, in beaker, stir, Yi Bian directly drop into 4% aluminum isopropylate/IPA solution 20g with 140rpm.Obtain the aluminium oxide nano particle dispersion.

Use has been used the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of laser Doppler method and has been measured size-grade distribution, and volume average particle size is 3200nm as a result, and the CV value of its size-grade distribution is 140%.

(Comparative Example E 2)

To be adjusted to the aqueous solution 20g of pH2 on one side with aqueous hydrochloric acid, in beaker, stir, Yi Bian directly drop into 10% aluminum isopropylate/IPA solution 20g with 140rpm.Obtain the aluminium oxide nano particle dispersion.

Use has been used the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of laser Doppler method and has been measured size-grade distribution, and volume average particle size is 5500nm as a result, and the CV value of its size-grade distribution is 150%.

The above results is shown in table 11.

[table 11]

Then; Use shown in Fig. 1 (A) can be near the reaction unit that each other evenly mixes in the subtend film fluid of processing with face 1, formation between 2 that set, that a few side is rotated with respect to the opposing party discretely; The zinc nitrate ethanolic soln is collaborated with the KOH ethanolic soln in the film fluid, on one side one side uniform mixing carries out evolution reaction in the film fluid.

(embodiment E 5)

On one side will be as the 1st fluidic BYK-190/0.08N KOH ethanolic soln from central authorities; To supply with pressure/back pressure=0.06MPa/0.005Mpa, rotating speed 1000rpm, 23 ℃ of liquor chargings of liquor charging temperature; To import processing with face 1, between 2 with 6ml/min as the ethanolic soln of the 2nd fluidic zinc nitrate 6 hydrates on one side.Nanoparticle dispersion liquid is from handling with face 1, being discharged between 2.

Secondly, with the nanoparticle dispersion liquid that obtains, with the condition spinning of 1,000,000 G * 10 minute, the operation of removing the also light impurity of ratio nano particle repeatedly.Then, after cleaning with pure water, use the observable nanoparticle of transmission electron microscope (TEM).From wherein selecting 100 particles arbitrarily, measure average primary particle diameter, the result is 11nm.The TEM photo of the particulate that obtains is shown in Figure 39.In addition; With the nanoparticle dispersion liquid lyophilize that obtains; Use X-ray diffraction device (full-automatic many purposes X-ray diffraction device that PANalytivacl society makes, X ' Pert PRO MPD) to resolve the nanoparticle powder that obtains, results verification is a zinc oxide nano-particle for obtaining nanoparticle.

And; The zinc oxide nano-particle powder that obtains is dropped in the ion exchanged water once more, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system); The result obtains the zinc oxide nano-particle dispersion liquid once more; Identical before average primary particle diameter and the vacuum lyophilization, average primary particle diameter is 11nm, and the redispersibility of confirming as the zinc oxide nano-particle powder that obtains is good.

(Comparative Example E 3)

With BYK-190/0.08N KOH ethanolic soln 100g, in beaker, stir, on one side Yi Bian drop into the ethanolic soln 20g of zinc nitrate 6 hydrates with 23 ℃ of solution temperatures, 300rpm.Obtain the zinc oxide nano-particle dispersion liquid.

Secondly,, carry out spinning, remove the operation of the impurity also lighter repeatedly than zinc oxide nano-particle with the condition of 1,000,000 G * 10 minute with the zinc oxide nano-particle dispersion liquid that obtains.Then, after cleaning with pure water, use transmission electron microscope (TEM) to observe zinc oxide nano-particle.From wherein selecting 100 particles arbitrarily, measure average primary particle diameter, the result is 381nm.

Can know by above content; Use can be near the mutual zinc oxide fine particles that obtains with the reaction unit that evenly mixes in the film fluid that forms between face of subtend processing that set, that at least one side is rotated with respect to the opposing party discretely; Be the particulate of nano-scale, redispersibility is excellent simultaneously.

(F, G) semiconductive particles

Below, the reaction that generates for compound semiconductor particulate of the present invention describes.

This reaction, like Fig. 1 (A) and meanwhile shown device, can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, between 2 by the strong hand uniform mixing take place.

At first; From the 1st d1 of importing portion as 1 stream; To contain at least a kind of ionic first fluid that has as the element of raw semiconductor as the 1st fluidic; Importing can be near each other the subtend configuration, that at least one side is rotated with respect to the opposing party processing discretely with face 1, between 2, the film fluid that generation is made up of the 1st fluid between this processing is with face.

Then; From the 2nd d2 of importing portion as other stream; Will as the 2nd fluidic contain at least a kind with above-mentioned first fluid in the ion that contains different types of, have ionic second fluid as the element of raw semiconductor, directly import the above-mentioned film fluid that constitutes by the 1st fluid.

As stated, through fluidic supply pressure and the processing that is being rotated with face between applied pressure pressure equilibrium and with fixed distance processing with face 1, between 2, the 1st fluid and the 2nd fluid interflow and form the film fluid.In this film fluid, the 1st fluid and the 2nd fluid are mixed, and above-mentioned 2 kinds of ions are reacted.More specifically, can separate out the reaction of carrying out the generation of compound semiconductor particulate through co-precipitation.

What explain is, owing to can carry out above-mentioned reaction with face 1, between 2 and get final product handling, therefore, also can import the 2nd fluid from the 1st d1 of importing portion on the contrary with above-mentioned, imports the 1st fluid from the 2nd d2 of importing portion.That is, the appellation of the what is called the 1st, the 2nd in each fluid is that the fluidic n of a plurality of existence of expression is individual, and just also can there be the fluid more than the 3rd in the mark in order to discern.

In addition, also can be only in any one of the 1st fluid and the 2nd fluidic, contain the ion that has as the element of raw semiconductor.And, can in the 1st fluid and the 2nd fluidic two sides, containing identical ion.

The particle diameter of the compound semiconductor particulate that obtains, single dispersity, or the control of crystal type can be through change handling with the rotating speed of face 1,2 or processing with face 1, distance and film flow rate of fluid or temperature between 2, and perhaps material concentration etc. is regulated.

In addition as above-mentioned the 1st fluid; Can use in the reversed micelle solution that in organic solvent, has added dispersion agent (following illustration) and water; Add and to contain at least a kind and have the 1st reversed micelle solution that obtains as the ionic aqueous solution of the element of raw semiconductor; As above-mentioned the 2nd fluid, can use contain at least a kind with above-mentioned the 1st reversed micelle solution in the ion that contained different types of, have ionic the 2nd reversed micelle solution as the element of raw semiconductor.That is, can use reversed micelle manufactured compound semiconductor particulate.

Though, do not do special qualification to the compound semiconductor particulate that the method for manufacture with compound semiconductor particulate of the present invention obtains.But preferably, can enumerate the II-VI compound semiconductor, the III-V compound semiconductor, the IV compound semiconductor, any one compound semiconductor particulate in the I-III-VI compound semiconductor, particularly, ZnO, ZnS, ZnSe; ZnTe, CdO, CdS, CdMnS, CdSe, CdMnSe, CdTe; CdMnTe, HgS, HgSe, HgTe, InP, InAs, InSb; InN, GaN, GaP, GaAs, GaSb, TiO ₂, WO ₃, PbS, PbSe, MgTe, SiC, SiGe, AlAs, AlP, AlSb, AlS, AlGaAS, InGaAs, InGaP, InAlAs, InGaAlP, InGaAsP, InGaN.

And, with the compound semiconductor particulate that the method for manufacture of compound semiconductor particulate of the present invention obtains, can enumerate carbon; Silicon, germanium, the monomer of periodictable the 14th family's element of tin etc.; The monomer of periodictable the 15th family's element of phosphorus (black phosphorus) etc.; The monomer of periodictable the 16th family's element of selenium, tellurium etc., the compound that a plurality of periodictable the 14th family's elements such as silit (SiC) form, White tin oxide (IV) (SnO ₂), tin sulfide (II, IV) (Sn (II) Sn (IV) S ₃), tin sulfide (IV) (SnS ₂), tin sulfide (II) (SnS), Tin diselenide (II) (SnSe), tellurium tin (II) (SnTe), lead sulfide (II) is (PbS); Lead selenide (II) (PbSe), periodictable the 14th family's element that lead telluride (II) (PbTe) waits and the compound of periodictable the 16th family's element, SP 1 (BN), boron phosphide BP (BP), arsenic boron (BAs); Aluminium nitride AlN (AlN), aluminium phosphide (AlP), aluminium arsenide (AlAs), aluminium antimonide (AlSb), gan (GaN); Gallium phosphide (GaP), gallium arsenide (GaAs), gallium antimonide (GaSb), indium nitride (InN); Indium phosphide (InP), indium arsenide (InAs), the belonging to group 13 of periodic table element of indium antimonide (InSb) etc. and the compound of periodictable the 15th family's element, aluminium sulfide (Al ₂S ₃), aluminum selenide (Al ₂Se ₃), sulfuration gallium (Ga ₂S ₃), gallium selenide (Ga ₂Se ₃), tellurium gallium (Ga ₂Te ₃), Indium sesquioxide (In ₂O ₃), indium sulfide (In ₂S ₃), indium selenide (In ₂Se ₃), tellurium indium (In ₂Te ₃) the belonging to group 13 of periodic table element that waits and the compound of periodictable the 16th family's element, thallium chloride (I) (TlCl), thallium bromide (I) (TlBr), the belonging to group 13 of periodic table element that thallium iodide (I) (TlI) waits and the compound of periodictable the 17th family's element; Zinc oxide (ZnO), zinc sulphide (ZnS), zinc selenide (ZnSe); Zinc telluridse (ZnTe), Cadmium oxide (CdO), Cadmium Sulfide (CdS); Cadmium selenide (CdSe), cadmium telluride (CdTe), zunsober (HgS); Mercury selenide (HgSe), periodictable the 12nd family's element of tellurium mercury (HgTe) etc. and the compound of periodictable the 16th family's element, red arsenic (III) (As ₂S ₃), arsenic selenide (III) (As ₂Se ₃), arsenic telluride (III) (As ₂Te ₃), ANTIMONY SULPHIDE (III) (Sb ₂S ₃), antimony selenide (III) (Sb ₂Se ₃), antimony telluride (III) (Sb ₂Te ₃), bismuth sulfide (III) (Bi ₂S ₃), bismuth selenide (III) (Bi ₂Se ₃), Tellurobismuthite (III) (Bi ₂Te ₃) periodictable the 15th family's element of waiting and the compound of periodictable the 16th family's element, cupric oxide (I) (Cu ₂O) etc. periodictable the 11st family's element and the compound of periodictable the 16th family's element; Cupric chloride (I) (CuCl), cupric bromide (I) (CuBr), cupric iodide (I) is (CuI); Silver monochloride (AgCl); Periodictable the 10th family's element that periodictable the 11st family's element of Silver monobromide (AgBr) etc. and the compound of periodictable the 17th family's element, nickel oxide (II) (NiO) wait and the compound of periodictable the 16th family's element, powder blue (II) is (CoO); Periodictable the 9th family's element that cobaltous sulfide (II) (CoS) waits and the compound of periodictable the 16th family's element, Z 250 (Fe ₃O ₄), periodictable the 7th family's element that periodictable the 8th family's element that iron sulphide (II) (FeS) waits and the compound of periodictable the 16th family's element, manganese oxide (II) (MnO) wait and the compound of periodictable the 16th family's element, moly-sulfide (IV) (MoS ₂), Tungsten oxide 99.999 (IV) (WO ₂) periodictable the 6th family's element of waiting and the compound of periodictable the 16th family's element, vanadium oxide (II) (VO), vanadium oxide (IV) (VO ₂), tantalum oxide (V) (Ta ₂O ₅) periodictable the 5th family's element of waiting and the compound of periodictable the 16th family's element, titanium oxide (TiO ₂, Ti ₂O ₅, Ti ₂O ₃, Ti ₅O ₉Deng) etc. periodictable the 4th family's element and the compound of periodictable the 16th family's element, magnesium sulfide (MgS), periodictable the 2nd family's element of magnesium selenide (MgSe) etc. and the compound of periodictable the 16th family's element, Cadmium oxide (II) chromium (III) (CdCr ₂O ₄), cadmium selenide (II) chromium (III) (CdCr ₂Se ₄), cupric sulfide (II) chromium (III) (CuCr ₂S ₄), mercury selenide (II) chromium (III) (HgCr ₂Se ₄) the chalcogen spinels that waits, barium titanate (BaTiO ₃) etc.

The element of the element monomer of above-mentioned example or formation compound promptly, is the element as raw semiconductor, in fluid, exists as the ion that contains this element.What explain is, in the present invention, is sulphur (S) source in the following ZnS particulate as the element of this raw semiconductor, like H ₂The such gas of S is the same, in fluid, exists also with the form beyond the ion and is allowed.

Among the present invention; In can method of manufacture near the compound semiconductor particulate in the film fluid that each other forms between subtend treated side that set, that at least one side is rotated with respect to the opposing party discretely; Use under the situation of coprecipitation method, for example under the situation of making the ZnS particulate, at first; The aqueous solution that uses the acetate that dissolved zinc (Zn) in the water system solvent or nitrate salt etc. has dissolved like sodium sulphite (Na in the 2nd fluid through using as the 1st fluid ₂S) the ZnS particulate can be synthesized in sulphur (S) source of the aqueous solution in such sulphur (S) source or the gas as hydrogen sulfide (H2S).At this moment, if in the above-mentioned aqueous solution, add the manganese (Mn) as activating element (activating element), copper (Cu), silver (Ag); Terbium (Tb), thulium (Tm), europium (Eu), samarium (Sm); Fluorine (F), chlorine (Cl), aluminium (Al) etc. are owing to these elements are on the ZnS particulate, to add as acvator; Can make it have the difference inherent characteristics of luminescence in addition,, not do special qualification, can use the Purified Water of ion exchanged water and pure water etc. as above-mentioned water system solvent; Alcohol or methyl alcohol, the organic solvent of toluene or YLENE etc., or its mixed solvent.Under the situation of mixed solvent, can be evenly compatible solution, also can be the suspension-s of non-conforming.And for the purpose of the solubleness of regulating the product behind the coprecipitation reaction, the alcohols that also can add methyl alcohol etc. waits to be implemented.

In addition, also can in above-mentioned fluid, add dispersion agent.In above-mentioned situation, this dispersion agent at the ZnS microparticle surfaces by coordination.As dispersion agent; Can use following material to implement: the Tripyrophosphoric acid class of six phosphoric acid, eight phosphoric acid, four phosphoric acid, triphosphoric acid etc.; The polymeric organic acid or the such macromolecule organic of Vinylpyrrolidone polymer, Z 150PH or Sodium hexametaphosphate 99 of acetate, vinylformic acid and methylacrylic acid etc., 2 mercapto ethanol, Thiovanic acid, 2-mercaptoethylamine, β-thiodiglycol, 2; 2 '-thio-alcohol of thiodiglycolic acid etc.; Or PS, or the various water soluble organic substances of phosphinoxides, or aerosol OT (AOT).

And, in order to promote the coordination of organic ligand, can be with handling with heating (heating) between face, or to processing with irradiation ultraviolet radiation between face (UV).Particularly, be provided with under the situation of temperature head with face 2 with face 1 and the 2nd processing,, therefore have to make thus and react promoted advantage owing to can in the film fluid, convection current take place in the 1st processing.

In addition simultaneously, the pH when reacting in order to adjust can add pH adjustment agent.Reaction conditions is under the situation of alkalescence, as pH adjustment agent, can use aqueous sodium hydroxide solution or potassium hydroxide solution, calcium hydroxide aqueous solution, baryta water, the strong basicity of ammoniacal liquor etc. or the weakly alkaline aqueous solution.

Reaction conditions is under the tart situation, as pH adjustment agent, can use aqueous hydrochloric acid or salpeter solution, the strongly-acid or the weakly acidic aqueous solution of acetic acid aqueous solution or aqueous citric acid solution etc.

Like this, can be manufactured on and be dispersed with average primary particle diameter 1～30nm, preferred 1～10nm, the more preferably aqueous dispersion (suspension-s) of the ZnS particulate of 2～7nm in the water system solvent.And; In the aqueous solution of acetate that has dissolved Zn or nitrate salt etc., add under the situation of above-mentioned dispersion agent; Can make and be dispersed with that dispersion agent is by the aqueous dispersion of coordinate ZnS particulate (suspension-s) from the teeth outwards, the redispersibility of the compound semiconductor particulate that obtains becomes very good.

As stated, remove the 1st d1 of importing portion, beyond the 2nd d2 of importing portion; The 3rd d3 of importing portion also can be set on treatment unit, under this situation, for example can be from each importing portion; PH is adjusted agent, have the ionic aqueous solution as the raw semiconductor element, dispersion agent imports in the treatment unit respectively.Like this, but each manages concentration, the pressure of each solution, can more critically control the reaction that the compound semiconductor particulate generates.Even under the situation that is provided with the importing portion more than the 4th, the fluid sectionalization that equally also can be so will import to treatment unit.

If replace Zn salt, can make the aqueous dispersion (suspension-s) that is dispersed with the compound semiconductor particulate that forms by Cadmium Sulfide (CdS) sulfides here, with the salt of cadmium (Cd) etc.And, through adding selenium (Se) source as sodium selenide (Na2Se), replace like sodium sulphite (Na ₂S) aqueous dispersion (suspension-s) that is dispersed with the compound semiconductor particulate that is formed by zinc selenide (ZnSe), cadmium selenide selenide such as (CdSe) is made in such sulphur (S) source.

And, can replace like sodium sulphite (Na through adding oxygen (O) source as sodium hydroxide (NaOH) ₂S) such sulphur (S) source can be made and is dispersed with by zinc oxide (ZnO) aqueous dispersion (suspension-s) of the compound semiconductor particulate that Cadmium oxide oxide compounds such as (CdO) forms.

In addition; In the present invention; Can be near discretely each other in the method for manufacture of the compound semiconductor particulate in the film fluid that forms between with face of subtend processing that set, that at least one side is rotated with respect to the opposing party; Use under the situation of reversed micelle method, also with the situation of above-mentioned coprecipitation method under roughly the same.For example, under the situation of making the ZnS particulate, as the 1st fluid at suitable organic solvent; For example; Add entry and suitable dispersion agent, two (2-ethylidene hexylidene) aerosol OTs ((below, be called AOT) for example in the heptane), make reversed micelle solution.In this reversed micelle solution, add aqueous zinc acetate solution, make the reversed micelle solution that contains zinc.Secondly, contain just like sodium sulphite (Na through use ₂S) the reversed micelle solution in such sulphur (S) source obtains containing the suspension-s of ZnS particulate as the 2nd fluid.At this moment, if in above-mentioned reversed micelle solution, add the manganese (Mn) as activating element, copper (Cu), silver (Ag); Terbium (Tb), thulium (Tm), europium (Eu); Samarium (Sm), fluorine (F), chlorine (Cl); Aluminium (Al) etc. owing to these elements are to add as the acvator to the ZnS particulate, can make it have the inherent characteristics of luminescence respectively.

Below, describe in more detail for disclosed embodiment of the present invention.But the present invention has more than and is defined in these embodiment.

What explain is; In following embodiment; So-called " from central authorities "; Refer to such an extent that be the meaning of " from the 1st d1 of importing portion " of treatment unit shown in above-mentioned, Fig. 1 (A), the 1st fluid is meant that the above-mentioned the 1st is processed liquid, that the 2nd fluid is meant is above-mentioned, treatment unit shown in Fig. 1 (A) " that import from the 2nd d2 of importing portion, above-mentioned the 2nd is processed liquid.

(embodiment F 1)

Use as Fig. 1 (A) shown in, can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with the device that evenly mixes reaction in the film fluid of face 1, formation between 2; With the zinc-manganese mixed aqueous solution in the film fluid with sodium sulfide solution interflow, on one side uniform mixing carry out coprecipitation reaction on one side.

On one side from central authorities with the 0.2mol/L aqueous zinc acetate solution, having added manganous acetate 4 hydrates and made the amount of manganese become the solution of 0.5 atom % (atm%) with respect to the amount of zinc as the 1st fluidic; To supply with pressure/back pressure=0.20MPa/0.01Mpa, rotating speed 500rpm, 25 ℃ of liquor chargings of liquor charging temperature; Make in the 0.4mol/L sodium sulfide solution, having added 2 mercapto ethanol on one side and import processing with face 1, between 2 with 10ml/min by the solution that reaches 1.0mol/L as the 2nd fluidic.Mn adds the ZnS microparticle dispersion and is discharged from face from handling.

Secondly, take Mn to add the ZnS particulate from this dispersion-s with dialysis tubing, use transmission electron microscope (TEM), the Mn that observes in this dispersion liquid adds the ZnS particulate.From wherein selecting 100 particles arbitrarily, measure average primary particle diameter, the result is 4nm.

Then, from this dispersion liquid, use vacuum freeze-drying method and remove solvent.The Powdered Mn that obtains is added the light of ZnS particulate irradiation 334nm wavelength, use spectrophotofluorometer (FP-777, Japanese beam split society system) to measure the luminescent spectrum that excites.Fluorescence intensity is shown as good value.

And; The pulverous Mn that obtains is added the ZnS particulate drop into once more in the ion exchanged water, stir with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system); The result obtains Mn once more and adds the ZnS particle dispersion liquid; Identical before average primary particle diameter and the vacuum lyophilization, average primary particle diameter is 4nm, and the redispersibility of confirming as the compound semiconductor particulate powder that obtains is good.

(embodiment F 2)

On one side from central authorities with the 0.2mol/L aqueous zinc acetate solution, having added manganous acetate 4 hydrates and made the amount of manganese become the solution of 0.5 atom % (atm%) with respect to the amount of zinc as the 1st fluidic; To supply with pressure/back pressure=0.40MPa/0.01Mpa, rotating speed 500rpm, 25 ℃ of liquor chargings of liquor charging temperature; Make in the 0.4mol/L sodium sulfide solution, having added 2 mercapto ethanol on one side and import processing with face 1, between 2 with 10ml/min by the solution that reaches 1.0mol/L as the 2nd fluidic.Mn adds the ZnS microparticle dispersion and is discharged from face from handling.

Secondly, take Mn to add the ZnS particulate from this dispersion-s with dialysis tubing, use transmission electron microscope (TEM), the Mn that observes in this dispersion liquid adds the ZnS particulate.From wherein selecting 100 particles arbitrarily, measure average primary particle diameter, the result is 6nm.

And, with the method identical, the pulverous Mn that obtains is added the ZnS particulate drop in the ion exchanged water once more with embodiment F 1; With high-speed stirring type dispersion machine (trade(brand)name: ClearMix; M technology society system) stir, the result obtains Mn once more and adds the ZnS particle dispersion liquid, and is identical before average primary particle diameter and the vacuum lyophilization; Average primary particle diameter is 6nm, and the redispersibility of confirming as the compound semiconductor particulate powder that obtains is good.

(embodiment F 3)

On one side from central authorities with the 0.2mol/L aqueous zinc acetate solution, having added manganous acetate 4 hydrates and made the amount of manganese become the solution of 0.5 atom % (atm%) with respect to the amount of zinc as the 1st fluidic; To supply with pressure/back pressure=0.40MPa/0.01Mpa, rotating speed 500rpm, 45 ℃ of liquor chargings of liquor charging temperature; Make in the 0.4mol/L sodium sulfide solution, having added 2 mercapto ethanol on one side and import processing with face 1, between 2 with 10ml/min by the solution that reaches 1.0mol/L as the 2nd fluidic.Mn adds the ZnS microparticle dispersion and is discharged from face from handling.

Secondly, take Mn to add the ZnS particulate from this dispersion-s with dialysis tubing, use transmission electron microscope (TEM), the Mn that observes in this dispersion liquid adds the ZnS particulate.From wherein selecting 100 particles arbitrarily, measure average primary particle diameter, the result is 4nm.

And, with the method identical, the pulverous Mn that obtains is added the ZnS particulate drop in the ion exchanged water once more with embodiment F 1; With high-speed stirring type dispersion machine (trade(brand)name ClearMix; M technology society system) stir, the result obtains Mn once more and adds the ZnS particle dispersion liquid, and is identical before average primary particle diameter and the vacuum lyophilization; Average primary particle diameter is 4nm, and the redispersibility of confirming as the compound semiconductor particulate powder that obtains is good.

(embodiment F 4)

On one side from central authorities with the 0.2mol/L aqueous zinc acetate solution, having added manganous acetate 4 hydrates and made the amount of manganese become the solution of 0.5 atom % (atm%) with respect to the amount of zinc as the 1st fluidic; Carry out liquor charging for 25 ℃ with supply pressure/back pressure=0.20MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature; Make in the 0.4mol/L sodium sulfide solution, having added 2 mercapto ethanol on one side and import processing with face 1, between 2 with 10ml/min by the solution that reaches 1.0mol/L as the 2nd fluidic.Mn adds the ZnS microparticle dispersion and is discharged from face from handling.

Secondly, take Mn to add the ZnS particulate from this dispersion-s with dialysis tubing, use transmission electron microscope (TEM), the Mn that observes in this dispersion liquid adds the ZnS particulate.From wherein selecting 100 particles arbitrarily, measure average primary particle diameter, the result is 10nm.

And, with the method identical, the pulverous Mn that obtains is added the ZnS particulate drop in the ion exchanged water once more with embodiment F 1; With high-speed stirring type dispersion machine (trade(brand)name: ClearMix; M technology society system) stir, the result obtains Mn once more and adds the ZnS particle dispersion liquid, and is identical before average primary particle diameter and the vacuum lyophilization; Average primary particle diameter is 10nm, and the redispersibility of confirming as the compound semiconductor particulate powder that obtains is good.

(embodiment F 5)

On one side from central authorities with the 0.2mol/L aqueous zinc acetate solution, having added manganous acetate 4 hydrates and made the amount of manganese become the solution of 0.5 atom % (atm%) with respect to the amount of zinc as the 1st fluidic; Carry out liquor charging for 52 ℃ with supply pressure/back pressure=0.20MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature; Make in the 0.4mol/L sodium sulfide solution, having added 2 mercapto ethanol on one side and import processing with face 1, between 2 with 10ml/min by the solution that reaches 1.0mol/L as the 2nd fluidic.Mn adds the ZnS microparticle dispersion and is discharged from face from handling.

Secondly, take Mn to add the ZnS particulate from this dispersion-s with dialysis tubing, use transmission electron microscope (TEM), the Mn that observes in this dispersion liquid adds the ZnS particulate.From wherein selecting 100 particles arbitrarily, measure average primary particle diameter, the result is 4nm.

And, with the method identical, the pulverous Mn that obtains is added the ZnS particulate drop in the ion exchanged water once more with embodiment F 1; With high-speed stirring type dispersion machine (trade(brand)name: ClearMix; M technology society system) stir, the result obtains Mn once more and adds the ZnS particle dispersion liquid, and is identical before average primary particle diameter and the vacuum lyophilization; Average primary particle diameter is 4nm, and the redispersibility of confirming as the compound semiconductor particulate powder that obtains is good.

(Comparative Example F 1)

Make the amount of manganese become the solution 20g of 0.5 atom % (atm%) with respect to the amount of zinc with in the 0.2mol/L aqueous zinc acetate solution, having added manganous acetate 4 hydrates on one side; In beaker; Condition with 25 ℃ of solution temperatures, rotating speed 300rpm stirs; Be dropped on one side and added 2 mercapto ethanol in the 0.4mol/L sodium sulfide solution and the feasible solution 20g that reaches 1.0mol/L, obtain Mn and add the ZnS microparticle dispersion.From the Mn interpolation ZnS microparticle dispersion that obtains, take Mn to add the ZnS particulate with dialysis tubing, use transmission electron microscope (TEM), the Mn that observes in this dispersion liquid adds the ZnS particulate.From wherein selecting 100 particles arbitrarily, measure average primary particle diameter, the result is 950nm.And; With the method identical, the pulverous Mn that obtains is added the ZnS particulate drop into once more in the ion exchanged water, with high-speed stirring type dispersion machine (trade(brand)name: ClearMix with embodiment F 1; M technology society system) stirs; The result obtains Mn once more and adds the ZnS microparticle dispersion, still, observes Mn and adds the strong agglutinative appearance of ZnS particulate.

The above results is shown in table 12.What explain is that embodiment 1～5 in the table and comparative example 1 are represented the foregoing description F1～F5 and Comparative Example F 1 respectively.

[table 12]

Below, semiconductive particles of the present invention is described through the reaction that reduction generates.

This reaction, Fig. 1 (A) shown device, can near discretely each other subtend set, at least one side with respect to the processing of the opposing party's rotation with face 1, between 2, on one side one side uniform mixing takes place by the strong hand.

At first; From the 1st d1 of importing portion as 1 stream; The first fluid that will contain at least a reductive agent as the 1st fluidic; Importing can be near each other the subtend configuration, that at least one side is rotated with respect to the opposing party processing discretely with 1,2 in face, the film fluid that generation is made up of the 1st fluid between this processing is with face.

Then,, will contain at least a fluidic second fluid that contains the compound of semiconductor element, directly import the above-mentioned film fluid that constitutes by the 1st fluid as the 2nd fluidic from the 2nd d2 of importing portion as other stream.

As stated, through fluidic supply pressure and the processing that is being rotated with face between applied pressure pressure equilibrium and with fixed distance processing with face 1, can form the film fluid between 2.And in this film fluid, the 1st fluid and the 2nd fluid interflow, mixed react the compound and the reductive agent that contain above-mentioned semiconductor element.More specifically, can carry out the semiconductor element reduction is generated the reaction of semiconductive particles.

What explain is, owing to can carry out above-mentioned reaction with face 1, between 2 and get final product handling, therefore, also can import the 2nd fluid from the 1st d1 of importing portion on the contrary with above-mentioned, imports the 1st fluid from the 2nd d2 of importing portion.That is, the appellation of the what is called the 1st, the 2nd in each fluid is that the fluidic n of a plurality of existence of expression is individual, and just also can there be the fluid more than the 3rd in the mark in order to discern.

In addition, the compound that also can be only in any of the 1st fluid and the 2nd fluidic, contains semiconductor element.Can in the 1st fluid and the 2nd fluidic two sides, contain the compound of identical semiconductor element.

The particle diameter of the semiconductive particles that obtains, single dispersity, or the control of crystal type can be through change handling with the rotating speed of face 1,2 or processing with face 1, distance and film flow rate of fluid or temperature between 2, and perhaps material concentration etc. is regulated.

In addition, as above-mentioned the 1st fluid, also can use in organic solvent, to have added and contain the 1st reversed micelle solution that at least a kind of dispersion agent (following illustration) obtains with the aqueous solution (polar liquid) of reductive agent.As above-mentioned the 2nd fluid, also can use in organic solvent, to have added and contain the 2nd reversed micelle solution that at least a kind of dispersion agent obtains with containing the aqueous solution (polar liquid) of the compound of semiconductor element.That is, also can use reversed micelle manufactured semiconductive particles.

Among the present invention; As can be near the mutual mode of the method for manufacture of the semiconductive particles in the film fluid that forms between with face of subtend processing that set, that at least one side is rotated with respect to the opposing party discretely; For example, make under the situation of silicon particle, through using the reductant solution that in the solvent of water etc., has dissolved hydrazonium sulfate etc. as the 1st fluidic; Reach the solution that has dissolved the silicon compound as silicon tetrachloride (SiCl4) as the 2nd fluidic, but the silicon particle of synthesis unit system.

As reductive agent, it is not done special the qualification, except that above-mentioned hydrazonium sulfate, for example, can enumerate Peng Qinghuana, inferior sodium phosphate; Hydrazine, the ion of transition metal (tervalent titanium ion, the cobalt ion of divalence etc.), methyl alcohol, ethanol, the alcohol of 2-propyl alcohol etc.; Or xitix etc., in addition, also can enumerate terepthaloyl moietie, gsh, organic acid (Hydrocerol A, oxysuccinic acid; Tartrate etc.), reductibility carbohydrate (glucose, semi-lactosi, seminose, fructose; Sucrose, SANMALT-S, raffinose, stachyose (etc.), and glycitols and Sorbitol Powder etc.In addition, also can use amine as reductive agent, related amine for example can be enumerated propylamine, butylamine, hexylamine, DIETHANOL AMINE, dipropyl amine, dimethylethyl amine; Diethylmethyl amine, triethylamine, quadrol, N,N,N, 1; The 3-diaminopropanes, N, N, N ', N '-tetramethyl--1,3-diaminopropanes, Triethylenetetramine (TETA), the fatty amine of TEPN etc.; Piperidines, N-methyl piperidine, piperazine, N, N '-lupetazin, tetramethyleneimine, N-crassitude, the ester ring type amine of morpholine etc.; Aniline, methylphenylamine, N, accelerine, Tolylamine, methyl oxyaniline, the aromatic amine of phenetidine etc., benzylamine, N-methylbenzylamine; N, N-dimethyl benzylamine, phenylethylamine, benzene dimethylamine, N, N, N ', the aralkyl amine of N '-tetramethyl-benzene n n dimetylaniline etc. etc.In addition, as above-mentioned amine, for example can enumerate methylamino ethanol, dimethylaminoethanol, trolamine; Thanomin, diethylolamine, methyldiethanolamine, Propanolamine; 2-(3-amino propyl amino) ethanol, butanolamine, hexanol amine, the alkanolamine of dimethylamino propyl alcohol etc.In addition, also can use basic metal naphthalene complex compound, EI ₂(E=such as samarium, ytterbium, the REE that europium is such), and, also can use as M ⁺Z ^-The metal complex of (the electrophilic molecule that Z=selects from aromatic molecule, M=basic metal) is implemented.Though do not do concrete special qualification,, except that basic metal naphthalene complex compound; Can enumerate basic metal biphenyl complex compound, basic metal 4,4 '-di-t-butyl biphenyl complex compound etc., alkali metal atom (lithium, sodium; Potassium etc.) and the basic metal aromatic hydrocarbons that forms by aromatic molecule, samarium diodide (SmI ₂), two iodate ytterbium (YbI ₂), two iodate europium (EuI ₂) the rare earth class iodide that wait.In addition, also can use magnesium anthracene complex compound.And, also can be with the use that combines of these reductive agents.In addition, also can implement to use LiBH ₄Or LiAlH ₄, LiBH (CH ₂CH ₃) ₃Wait and implement.Wherein, can use aptly according to purpose.And, though can use like lithium, sodium, potassium, the solid catalyst of the nonhomogeneous system that magnesium is such is implemented, and from handling consideration aspect the homogeneity between face, preferably uses the homogeneous system catalyzer.

As silicon compound, do not do special qualification, can use contain element silicon, silicon tetrachloride (SiCl ₄), bromination silane (SiBr ₄) halogenated silane (SiX that waits ₄, the X=halogen element), tetraethoxysilane (SiOEt ₄, the OEt=oxyethyl group) etc. organoalkoxysilane (SiOR ₄, the OR=alkoxyl group).Under the situation of making the semiconductive particles beyond the silicon, do not do special qualification, as semiconductor compound, can use germanium halide (GeX ₄), alkoxide germanium (GeOR ₄), tin halides (SnX ₄), alkoxide tin (SnOR ₄), the halocarbon (CX of carbon tetrabromide etc. ₄) etc.

In addition, when making semiconductive particles, be selected from above-mentioned silicon containing, germanium, carbon, and in the compound that forms of the semiconductor element of tin, the compound that contains as other element of activating element capable of being combined.As above-mentioned other element, do not do special qualification, for example, also can contain and be selected from lead through combination, titanium, vanadium, zirconium, hafnium, phosphorus, the compound of the metallic element of boron is made the semiconductive particles that contains these metallic elements.

As lead, titanium, vanadium, zirconium, and hafnium, phosphorus, the supply source of boron is not done special qualification, can use lead halide (PbX ₄), the plumbous (PbOR of alkoxide ₄), halogenated titanium (TiX ₄), alkyl dioxide (TiOR ₄), halogenation vanadium (VX ₄), zirconium halide (ZrX ₄), alkoxide zirconium (ZrOR ₄), halogenation hafnium (HfX ₄), alkoxide hafnium (HfOR ₄), halogenation boron (BX ₃) compound that waits.

At this moment, for example, can be through in comprising the fluid that contains the compound that the semiconductor element that formed by silicon forms, comprising germanium simultaneously, carbon, and tin contain the compound that above-mentioned other element forms, and the semiconductive particles that also can obtain multicomponent system is implemented.And; Through using reductive agent in the first fluid; Use in second fluid and comprise the fluid that contains the compound that the semiconductor element that formed by silicon forms; Use the fluid that contains the semiconductor element beyond the silicon as the 3rd fluid, also can the semi-conductor that the silicon particle surface forms with other semiconductor element be covered and implement.

In addition,, also can make water as solvent, ion exchanged water, the water system solvent of ultrapure water etc., toluene, YLENE, the organic solvent of alcohol etc. is implemented.

And, to make with the organic solvent system under the situation of semiconductive particles, above-mentioned reductive agent, silicon chlorides also can use nonreactive inertia organic solvent to implement, and select aptly corresponding to above-claimed cpd.As such organic solvent, for example, can use glycol dimethyl ether (below be designated as glyme), THF, Anaesthetie Ether has the solvent of ehter bond.

And, can heat (heating) or processing under cooling with between face, maybe can be to handling with irradiation ultraviolet radiation between face (UV), or irradiating microwaves, in addition also can be to processing with giving ultrasonic energy between face.Particularly, semiconductive particles gives the material of very big influence for the temperature environment when generating to its particle diameter or crystal type, through direct heating or cooling as the processing of film with between face, can carry out the temperature treatment in the reaction conditions tightly, be effective.In addition, be provided with under the situation of temperature head with face 2 with face 1 and the 2nd processing,, therefore have to make thus and react promoted advantage owing to can in the film fluid, convection current take place in the 1st processing.

More specifically, for heating (heating), as above-mentioned explained, for example with at least one side of portion 10,20 well heater and the big envelope through thermal medium are set through reason throughout, can heat (heating) film fluid.In addition, for irradiation ultraviolet radiation (UV), for example, reason is faced film fluid irradiation ultraviolet radiation (UV) with the element that 10,20 at least one sides of portion or two sides are provided with the lamp etc. of irradiation ultraviolet radiation from corresponding processing usefulness throughout.In addition, the microwave generating apparatus of the magnetron that has irradiating microwaves with at least one side or two sides of portion 10,20 through reason throughout etc. can carry out the heating of treat fluid, reacts promotion.In addition, for giving ultrasonic energy, for example, can manage throughout with 10,20 at least one sides of portion or two sides ultrasonic oscillator is set.

And; Through can guarantee to reduce pressure or the container of vacuum state in carry out above-mentioned reaction, make and handle 2 sides that back fluid (semiconductive particles dispersion liquid) is discharged from and form decompression or vacuum state; The degassing of the gas that carries out being contained in gas that each fluidic interflow in above-mentioned film fluid produced and the above-mentioned fluid, or above-mentioned fluidic desolventizing.Like this; Even with almost carrying out simultaneously of making that semiconductive particles the handles situation that desolventizing handles under; Discharge with atomize with face from handling because handle with the fluid that contains semiconductive particles between face, so this fluidic surface-area increase, desolventizing efficient is very high.Therefore than till now also simply, 1 operation is carried out semiconductive particles and is made and handle and the desolventizing processing in fact.

But also can in the container of filling rare gas element, carry out above-mentioned reaction, the dispersion liquid after under inert gas atmosphere, making processing ejects enforcement.Can prevent the reaction that in the intent of the present invention, do not have by compounds caused, that contain semiconductor element such as moisture in the atmosphere or oxygen.As above-mentioned rare gas element, be rare gas element as long as select it for raw material and reaction product according to purpose, do not do special restriction, for example can enumerate argon gas and nitrogen etc.

In addition, through carrying out above-mentioned reaction in the thermoregulator container, for example, can cool off fluid (semiconductive particles dispersion liquid) after the processing that just has been discharged from.Thus, can the semiconductive particles that obtain through reaction be cooled to the equilibrium temperature scope as particulate rapidly.In addition, through with heating in the container, also can improve the efficient that above-mentioned desolventizing is handled and the degassing is handled.

In addition simultaneously, the pH when reacting in order to adjust can add pH adjustment agent.Reaction conditions is under the situation of alkalescence, as pH adjustment agent, does not do special qualification, can use aqueous sodium hydroxide solution or potassium hydroxide solution, calcium hydroxide aqueous solution, baryta water, the strong basicity of ammoniacal liquor etc. or the weakly alkaline aqueous solution.Reaction conditions is under the tart situation, as pH adjustment agent, does not do special qualification, can use aqueous hydrochloric acid or salpeter solution, the strongly-acid or the weakly acidic aqueous solution of acetic acid aqueous solution or aqueous citric acid solution etc.Because reduction reaction receives the influence of the pH of solution, under the situation that semiconductive particles and reductive agent are reacted as the application invents, make effectively.

In addition, also can in above-mentioned fluid, add dispersion agent as required.Under above-mentioned situation, this dispersion agent on the semiconductive particles surface by coordination.As dispersion agent, do not do special qualification, under the situation that semiconductive particles is handled as dispersion liquid, for not aggegation of semiconductive particles in dispersion medium, or in order to change medicine, the fluorescence and the characteristics of luminescence etc. can be protected the surperficial material of semiconductive particles.For example, can use following material to implement: the Tripyrophosphoric acid class of six phosphoric acid, eight phosphoric acid, four phosphoric acid, triphosphoric acid etc., the polymeric organic acid or the Vinylpyrrolidone polymer of acetate, vinylformic acid and methylacrylic acid etc.; The macromolecule organic that Z 150PH or Sodium hexametaphosphate 99 are such, 2 mercapto ethanol, Thiovanic acid; 2-mercaptoethyl amine, β-thiodiglycol, 2; 2 '-thio-alcohol of thiodiglycolic acid etc., or the various organism of PS or phosphinoxides, or aerosol OT (AOT).

As stated, remove the 1st d1 of importing portion, beyond the 2nd d2 of importing portion; The 3rd d3 of importing portion also can be set on treatment unit, under this situation, for example can be from each importing portion; PH is adjusted agent, contain the solution of the compound of semiconductor element, reductive agent imports in the treatment unit respectively.Like this, but each manages concentration, the pressure of each solution, can more critically control the reaction that generates semiconductive particles.Even under the situation that is provided with the importing portion more than the 4th, the fluid sectionalization that equally also can be so will import to treatment unit.In addition; Between handling, generate and pass through with lithium with face; 4; 4 '-di-t-butyl biphenyl complex compound (below be designated as DBB) reacts as raw material with THF and obtains the such reductive agent of lithium DBB complex compound (below be designated as the LDBB complex compound), is about in the semiconductor element of reality that to synthesize before the reduction reaction also be effective.

Like this, can be manufactured in the water system solvent or be dispersed with average primary particle diameter in the organic solvent is 0.8～100nm, preferred 1～50nm, the dispersion liquid of the semiconductive particles of 1～20nm (suspension-s) most preferably.And; Add under the situation of above-mentioned dispersion agent being dissolved with reductive agent or containing in the solution of compound of semiconductor element; Can make be dispersed with dispersion agent from the teeth outwards by coordination the dispersion liquid (suspension-s) of semiconductive particles, it is very good that the redispersibility of the semiconductive particles that obtains becomes.The semiconductive particles that utilizes method of manufacture of the present invention to obtain can use in the purpose of solar cell etc.The semiconductive particles surface that will utilize method of manufacture of the present invention to obtain in addition carry out hydrophilization semiconductive particles, preferably in the mensuration of the environmental correclation material of the organism related substances of antigen, antibody, DNA etc., dioxin etc., use.In addition, disperseing semiconductive particles narrow particle size distribution single is the mark substance of antibody and situation about using is inferior as molecular recognition, can carry out the mensuration of very high degree of precision.As the purposes of semi-conductor nano particles of the present invention, can enumerate display equipment or luminescent lamp, the organism related substances detects the mark substance of usefulness etc.In addition, under the situation that the lower material of toxicity by silicon etc. forms, also can use in the cell imaging system that is used for studying the cell dynamic dispatching.

In addition; In the present invention; Can be near each other using under the situation of reversed micelle method in the method for manufacture of the semiconductive particles in the film fluid that forms between with face of subtend processing that set, that at least one direction is rotated for the opposing party discretely, also with above-mentioned situation under cardinal principle identical, for example; Under the situation of making silicon particle, use LiAlH ₄THF solution as the 1st fluid.Secondly, in suitable organic solvent (for example, toluene), add suitable dispersion agent (for example, four octyl brometo de amonio and silicon tetrachlorides) as the 2nd fluid.Through using reversed micelle solution, can obtain containing the suspension-s of silicon particle.At this moment, if in above-mentioned reversed micelle solution, add lead, titanium, vanadium; Zirconium, and by hafnium, phosphorus, the compound that boron forms is as activating element; Because therefore these elements can make it have the inherent characteristics of luminescence separately, fluorescent characteristic etc. as adding for the acvator of silicon particle.

In addition, the surface stabilization that also can carry out the gained semiconductive particles is handled and is implemented.So-called surface stabilization is handled, and is for example to prevent that in order to prevent reaction of moisture, surface because of in atmosphere, directly taking out in chlorine end-blocking semiconductive particles, surperficial chlorine atom and the atmosphere from becoming the processing that hydroxyl is the phenomenon of representative.If for example hydroxy-end capped silicon particle is in contact with one another, because of hydrolysis takes place easily for the heat of room temperature degree, the surface oxidation deterioration produces the gel organosilicon, thus surface stabilization to handle be important operation.

Method as surface stabilization is handled for example at first, is cooled to chlorine end-blocking silicon particle dispersion-s liquid near 0 ℃, slowly drips the diethyl ether solution of having dissolved bromination hexyl magnesium.After near 0 ℃ it being reacted, remove refrigerant, heat up naturally at room temperature, stir.Like this, generation is as alkyl (hexyl) the end-blocking silicon nano of object.

By product from solution is extracted alkyl-blocked silicon nano out, is made with extra care, can obtain as object by alkyl-blocked silicon nano.

In addition, handle, the method for use organolithium reagent etc. is arranged as such surface stabilization.The solution that will contain chlorine end-blocking silicon nano is cooled to 0 ℃, adds the diethyl ether solution of having melted hexyl lithium and stirs, and heats up naturally at room temperature, makes its reaction.Like this, with the same under the situation of above-mentioned use bromination hexyl magnesium, can generate alkyl (hexyl) end-blocking silicon nano.

In addition, also have in case after chlorine end-blocking silicon particle carried out the hydrogen end-blockingization, carry out surperficial end capped method again with the organic reagent (for example, alkene) that contains the two keys of carbon.The solution that will contain chlorine end-blocking silicon nano is cooled to 0 ℃, adds the glyme solution that has dissolved lithium aluminum hydride and stirs, and it is heated up at room temperature naturally, and make its reaction, thus hydrogen end-blocking silicon particle is carried out surface-treated.Secondly, add methyl alcohol, the unreacted lithium aluminum hydride of chilling.After this, add platinum chloride hydrochlorate aqueous isopropanol, react while continuation will reflux as a kind hexene of alkene as catalysts.Like this, the same with the situation of using above-mentioned Grignard reagent or organolithium reagent, can generate alkyl (hexyl) end-blocking silicon nano.

In addition, the functional group during surface stabilization is handled beyond the hexyl does not do special qualification, still, can enumerate following group.Wherein, can preferably use compound with carbon-to-carbon double bond C=C.

[Chemical formula 1]

C＝C、C＝O、C＝N、C≡N、C＝S、(HO)C＝O

As the above-mentioned molecule that carbon-to-carbon double bond is arranged endways, do not do special qualification, for example can enumerate general formula H ₂C=CH-(CH ₂) _N-1The molecule that-X is represented.Here, X representes functional group, and n representes positive integer.As the above-mentioned X of functional group, for example can enumerate-NR ₂,-NR ' R ,-NHR ,-NH ₂Deng amino ,-CR " R ' R ,-CR ' ₂R ,-CR ₃,-CHR ₂,-CHR ' R ,-CH ₂R ,-CH ₃,-SR ,-SH ,-I ,-Br ,-Cl ,-F.What explain is, here, R ", R ', R represent organic saturated compound base, or, nonreactive other reactive functional groups of Si-H of expression and particle surface.Under this situation, the compound that can further on particle surface, react through the reactive functional groups with other is implemented surface treatment.

In addition, as the above-mentioned molecule that has reactive functional groups endways,, can the semiconductive particles that obtain through above-mentioned reduction operation be carried out hydrophilization if use the molecule of responding property functional group endways and possess hydrophilic property base.As the molecule of above-mentioned functional group of responding property endways and possess hydrophilic property base, do not do special qualification, that for example can enumerate allylamine etc. has carbon-to-carbon double bond to combine and the molecule of possess hydrophilic property base etc. endways.

As on the surface of the semiconductive particles that obtains through above-mentioned reduction operation, making above-mentioned catalyst system therefor when having the molecular reaction of carbon-to-carbon double bond bonded endways, do not do special qualification, for example, can use H ₂PtCl ₆Deng.The kind of catalyzer in the reduction operation for example, can be chosen as aptly, after catalyzer adds, only stirs the material that can react at room temperature, the material that begins to react through light and heat etc. etc.

For aforesaid surface stabilization treatment procedures; The same with known method; Available general beaker or flask, groove etc. carry out the microparticle surfaces stabilization treatment from handle the semiconductive particles dispersion liquid that is discharged from face, and the surface stabilization that processing that also can be in the present invention reaches semiconductive particles with enforcement between face is handled and implemented.That is, as containing the fluid of reductive agent as the 1st fluidic, comprise the fluid of the compound that contains semiconductor element, and contain the fluid of surface treatment stablizer, implement whole processing with substantial 1 operation as the 3rd fluidic as the 2nd fluidic.

Below, describe in more detail for disclosed embodiment of the present invention.But the present invention has more than and is defined in these embodiment.

What explain is; In following embodiment; So-called " from central authorities "; Refer to such an extent that be the meaning of " from the 1st d1 of importing portion " of treatment unit shown in above-mentioned, Fig. 1 (A), the 1st fluid is meant that the above-mentioned the 1st is processed liquid, that the 2nd fluid is meant is above-mentioned, treatment unit shown in Fig. 1 (A) " that import from the 2nd d2 of importing portion, above-mentioned the 2nd is processed liquid.

(embodiment G1)

Use as Fig. 1 (A) shown in, can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with the device that evenly mixes reaction in the film fluid of face 1, formation between 2; Silicon compound is collaborated with reductive agent in the film fluid; On one side uniform mixing reduces silicon compound on one side, obtains silicon particle.

(adjustment of the 1st fluidic)

Take by weighing lithium 30mMol in the flask in advance, fully make its drying with argon gas.Then,, inject the anhydrous tetrahydro furan dissolved DBB 40mMol (below be referred to as THF) solution 200ml, use stirrer at room temperature through addition funnel, on one side stirring reaction solution, LDBB complex compound (LDBB/THF solution) generated on one side.

On one side will be as the LDBB/THF solution of the above-mentioned making of the 1st fluidic from central authorities; Carry out liquor charging to supply with pressure/back pressure=0.05MPa/0.01Mpa, rotating speed 500rpm, liquor charging temperature-50 ℃; To import processing with face 1, between 2 with 0.5ml/min as the 2nd fluidic silicon tetrachloride on one side.Imported silicon tetrachloride as the 2nd fluid on one side with face 1, between 2 with the 0.5ml/min processing.The dispersion liquid of silicon semiconductor particulate is discharged under ar gas environment.

Handle in order to carry out surface stabilization,, secondly slowly drip the diethyl ether solution of having dissolved bromination hexyl magnesium 20mMol near the liquid effluent temperature adjustment to 0 ℃.Making its reaction after about 30 minutes near 0 ℃, remove refrigerant, heat up naturally at room temperature, stirred 24 hours.Generation is as alkyl (hexyl) the end-blocking silicon nano of object.

In order from solution, alkyl-blocked silicon nano extraction to be made with extra care, then in flask, inject hexane 100ml, stir fully, silicon nano is dissolved fully.With this hexane solution that transfer pipet is extracted out, use separating funnel with pure water washing 3 times, remove remaining lithium salts, magnesium salts.The hexane solution of having washed passes in sal epsom and to dewater.Then, separate with post and to remove DBB and hexane respectively, obtain alkyl-blocked silicon particle as object.

Observed and transmission electron microscope observation by scanning electron microscope, the median size of confirming as the silicon part of alkyl-blocked silicon nano is about 2.5nm.Compositional analysis according to constituting element does not detect chlorine and oxygen, has therefore obtained highly purified particulate.

The fluorescent characteristic of the hexane solution of this alkyl-blocked silicon nano, ultraviolet ray excited through 350nm, obtaining the peak emission wavelength is the glimmering long spectrum of 450nm, the about 55nm of spectrum half breadth.With the rhodamine 6G pigment is that benchmark is tried to achieve fluorescence quantum efficiency, and the result is about 44% value.Thus, through synthesis method of the present invention, can obtain luminous silicon based semiconductor material effectively.

(embodiment G2～G4)

Embodiment G2～G4 with the order identical with embodiment G1, only change the liquor charging temperature and carry out.

The above results is shown in table 13.That explains is the embodiment 1～4 in the table, expression the foregoing description G1～G4.

[table 13]

(comparative example G1)

On one side will be as the LDBB/THF solution 20g that makes among the 1st fluidic the foregoing description G1, in beaker, stir with solution temperature-50 ℃, 300rpm, Yi Bian drop into silicon tetrachloride 20g.Obtain the dispersion liquid of silicon semiconductor particulate.The surface stabilization of the semiconductive particles that obtains handles, and from dispersion liquid, remove DBB and carry out with embodiment G1 with hexane identically.By electron microscope observation, and transmission electron microscope observation, the median size of confirming as the silicon part of alkyl-blocked silicon nano is about 44.2nm.

(embodiment G5)

Use as Fig. 1 (A) shown in, can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with the device that evenly mixes reaction in the film fluid of face 1, formation between 2; Use the reversed micelle method that silicon compound is collaborated with reductive agent in the film fluid; On one side uniform mixing reduces silicon compound on one side, obtains silicon particle.

On one side from central authorities with as the 1st fluidic, among toluene 100ml, add SiCl ₄92 μ l and four octyl group brometo de amonio 1.5g, use ClearMix 1.5S (M technology society system) obtain reversed micelle solution with 8000rpm stirring 10 minutes; Carry out liquor charging for 30 ℃ with supply pressure/back pressure=0.08MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature, on one side will be as the 2nd fluidic 1.0M LiAlH ₄/ THF solution imports with 1.0ml/min and handles with face 1, between 2.The dispersion liquid of silicon semiconductor particulate is discharged from.

In the dispersion liquid of the silicon semiconductor particulate that is discharged from, add methyl alcohol.In the semi-conductor nano particles solution that obtains, add 1-heptene 2mL and H ₂PtCl ₆0.1M Virahol 0.1mL solution, use ClearMix 1.5S (M technology society system) to stir 3 hours with 8000rpm.Making with extra care of the solution that obtains at first, removed toluene and heptene in the above-mentioned solution through Rotary Evaporators.Secondly, to wherein adding hexane, and then add positive NMF 2, transfer to separating funnel and stir, separate and make with extra care through transferring to unreacted reductive agent and tensio-active agent in the positive NMF.And then carry out 2 these positive NMFs and add later operation, obtained sealing the semiconductive particles that (capped) is made up of Si through the 1-heptene that is in the hexane.

(embodiment G6～G8)

The order that embodiment G6～G8 is identical with embodiment G5, only change rotating speed and supply pressure and carry out.

The above results is shown in table 14.That explains is the embodiment 5～8 in the table, expression the foregoing description G5～G8.

[table 14]

(comparative example G2)

In toluene 100ml, add SiCl ₄92 μ l and four octyl group brometo de amonio 1.5g; Use ClearMix 1.5S (M technology society system) to stir 10 minutes and obtain reversed micelle solution 20g, this is obtained reversed micelle solution 20g, in beaker with the condition of 8000rpm; Stir on one side with 30 ℃ of solution temperatures, 300rpm, Yi Bian drop into 1.0M LiAlH ₄/ THF solution 60g.In the semi-conductor nano particles solution that obtains, add 1-heptene 2mL and H ₂PtCl ₆0.1M Virahol 0.1mL solution, use ClearMix 1.5S (M technology society system) to stir 3 hours with 8000rpm.Making with extra care of the solution that obtains at first, removed toluene and heptene in the above-mentioned solution through Rotary Evaporators.Secondly, to wherein adding hexane, and then add positive NMF 2, transfer to separating funnel and stir, separate and make with extra care through transferring to unreacted reductive agent and tensio-active agent in the positive NMF.And then carry out 2 these positive NMFs and add later operation, through the semiconductive particles that constitutes by Si that is in that 1-heptene in the hexane obtained adding a cover.The median size of confirming as the semiconductive particles that is made up of Si is about 44.2nm.

(embodiment G9)

Use as Fig. 1 (A) shown in, can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with the device that evenly mixes reaction in the film fluid of face 1, formation between 2; Adopt the reversed micelle method that silicon compound is collaborated with reductive agent in the film fluid; On one side uniform mixing reduces silicon compound on one side, obtains silicon particle.

On one side will be as the 1st fluidic 0.1mol/L hydrazonium sulfate aqueous solution from central authorities; Carry out liquor charging for 80 ℃ with supply pressure/back pressure=0.20MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature; To import processing with face 1, between 2 with 1.0ml/min as the 2nd fluidic 0.1mol/L silicon tetrachloride aqueous solution on one side.The dispersion liquid of silicon semiconductor particulate is discharged from.After removing the impurity in the dispersion liquid, use transmission electron microscope (TEM), the silicon semiconductor particulate in this dispersion liquid is observed.From wherein choosing 100 particle assay average primary particle diameters arbitrarily, the result is 5.1nm.In addition, adopt spectrophotofluorometer FP-6500 (Japanese beam split society system), measure quantum yield, the result is 58%.Use LUMI-COUNTER 2500, be determined at 27 ℃ active oxygen formation speed, the result is 0.5ml/min/g.

(embodiment G10～G12)

Embodiment G10～G12 with the order identical with embodiment G9, only change the liquor charging temperature and carry out.

The above results is shown in table 15.That explains is the embodiment 9～12 in the table, expression the foregoing description G9～G12.

[table 15]

(comparative example G3)

With 0.1mol/L hydrazonium sulfate aqueous solution 20g, in beaker, stir with 30 ℃ of solution temperatures, 300rpm, on one side Yi Bian drop into 0.1mol/L silicon tetrachloride aqueous solution 20g.After removing the impurity in the dispersion liquid of the silicon semiconductor particulate that obtains, use transmission electron microscope (TEM), observe the silicon semiconductor particulate in this dispersion liquid.From wherein choosing 100 particle assay average primary particle diameters arbitrarily, the result is 33.5nm.

(H) titanium oxide ultra micron

Below, ultramicronized reaction describes to generation titanium oxide of the present invention.

This reaction, use like Fig. 1 (A) on one side shown device, can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, between 2 by the strong hand one side uniform mixing take place.

At first; From the 1st d1 of importing portion as 1 stream; To contain the fluid that is useful on the water system solvent that makes the titanium compound hydrolysis as the 1st fluidic; Importing can near separate and the subtend configuration, that at least one side is rotated with respect to the opposing party each other processing with 1,2 in face, the film fluid that generation is made up of the 1st fluid between this processing is with face.

Then,, will contain the fluid of at least a titanium compound, directly import the above-mentioned film fluid that constitutes by the 1st fluid as the 2nd fluidic from the 2nd d2 of importing portion as other stream.

As stated, through fluidic supply pressure and the processing that is being rotated with face between applied pressure pressure equilibrium and will be apart from the processing of having controlled with face 1, can form the film fluid between 2.And the 1st fluid and the 2nd fluid interflow is mixed in this film fluid, and titanium compound is hydrolyzed, and can carry out the reaction that the titanium oxide ultra micron generates (separating out)

What explain is, owing to can carry out above-mentioned reaction with face 1, between 2 and get final product handling, therefore, also can import the 2nd fluid from the 1st d1 of importing portion on the contrary with above-mentioned, imports the 1st fluid from the 2nd d2 of importing portion.That is, the appellation of the what is called the 1st, the 2nd in each fluid is that the fluidic n of a plurality of existence of expression is individual, and just also can there be the fluid more than the 3rd in the mark in order to discern.

In addition, only can be and contain titanium compound in the 1st fluid and any side of the 2nd fluidic.Also can be among the 1st fluid and the 2nd fluidic two sides and contain identical type or different types of titanium compound.

The ultramicronized particle diameter of the titanium oxide that obtains, single dispersity, or the control of crystal type can be through change handling with the rotating speed of face 1,2 or processing with face 1, distance and film flow rate of fluid or temperature between 2, and perhaps material concentration etc. is regulated.

As the fluidic solvent that contains at least a kind of above-mentioned titanium compound that the present invention uses, can select aptly like water, methyl alcohol, ethanol, acetone according to the kind and the reactive mode of the titanium compound that uses; N, N,N-DIMETHYLACETAMIDE, the water Combination organic solvent that methyl-sulphoxide is such; Like octane, hexanaphthene, benzene; YLENE, Anaesthetie Ether, the such water of ETHYLE ACETATE is the Combination organic solvent not.

In addition,, can use in organic solvent, to add the reversed micelle solution that dispersion agent (following illustration) obtains with water,, can use the non-aqueous solution that in non-water system solvent, contains at least a kind of titanium compound as above-mentioned the 2nd fluid as above-mentioned the 1st fluid.That is, can adopt the reversed micelle legal system to make the titanium oxide ultra micron.What explain is as above-mentioned the 2nd fluid, also can use the aqueous solution that contains titanium compound, the reversed micelle solution that contains titanium compound.

As above-mentioned titanium compound, do not do special qualification, can be from tetramethoxy titanium, purity titanium tetraethoxide); Four positive propoxy titaniums, tetraisopropoxy titanium, four titanium n-butoxide; Four isobutoxy titaniums, four titan-alkoxide or derivatives thereofs of four tert.-butoxy titaniums etc., titanium tetrachloride; The titanium sulfate acyl, the Hydrocerol A titanium, and choose a kind at least in four Titanium Nitrates and implement.

And, also can be in above-mentioned fluid at least a in contain metallic compound and implement, this metallic compound contains be solid-solubilized in the element (activating element) in titanium oxide different with above-mentioned titanium compound.As the above-mentioned titanium compound that is solid-solubilized in the element in the titanium oxide that contains, do not do special qualification, can enumerate and be selected from Al, Ba, Mg, Ca, La, Fe, Si, Zr, Pb; Sn, Zn, Cd, As, Ga, Sr, Bi, Ta, Se, Te; Hf, Ni, Mn, Co, S, Cr, V, Ge, Li, at least a kind alcoholate or the salt of B.And, for all elements of representing in the chemical periodictable, can be used as the above-mentioned compound that is solid-solubilized in the element in the titanium oxide that contains and use.

Like this; Through containing above-mentioned activating element, promptly mixing (doping), can the light maximum absorption wavelength of titanium oxide be moved to long wavelength side, can carry out the action of the titanium deoxide catalyst under visible light; Or improve as photocatalyst; Antiseptic-germicide, deodourizing agent, the performance of optical material, electronic material etc.

In addition, also can add dispersion agent at least one at above-mentioned fluidic.Under above-mentioned situation, this dispersion agent on the ultramicronized surface of titanium oxide by coordination.This dispersion agent is not done special qualification, can use like starch methylcellulose gum, the cellulose family that methylcellulose gum is such; The polyacrylamide imines, polyethylene oxide gathers the macromolecular dispersion stabilizer of (oxystearic acid-g-TEB 3K-altogether-methylacrylic acid) multipolymer etc., and nonionic is a tensio-active agent; Negatively charged ion is a tensio-active agent, amphoterics, or; Six phosphoric acid, eight phosphoric acid, four phosphoric acid; The Tripyrophosphoric acid class of triphosphoric acid etc., acetate, the polymeric organic acid of acrylic or methacrylic acid etc.; Like Vinylpyrrolidone polymer, the macromolecule organic that Z 150PH or sodium hexametaphosphate are such, or at least a enforcement the in the aerosol OT (AOT).

In addition, can be at above-mentioned fluidic pH when adjusting reaction and add pH adjustment agent at least one.It is not done special qualification, for example, is under the situation of alkalescence at reaction conditions, as pH adjustment agent, can use aqueous sodium hydroxide solution or potassium hydroxide solution; Calcium hydroxide aqueous solution, baryta water, TMAH, tetraethyl ammonium hydroxide, TPAOH; Tetrabutylammonium hydrogen oxygen ammonium, monoethanolamine, diethylolamine, trolamine; Tetramethyl ammonium chloride, etamon chloride, 4-propyl ammonium chloride, tetrabutylammonium chloride; Octylame, laurylamine, the amine of stearylamine etc. and the polymer amine and the salt thereof that form by this amine, and the strong basicity or the weakly alkaline aqueous solution of ammoniacal liquor etc.

At reaction conditions is under the tart situation, as pH adjustment agent, can use aqueous hydrochloric acid or aqueous nitric acid, the strongly-acid of acetic acid aqueous solution or aqueous citric acid solution etc. or the weakly acidic aqueous solution etc.Through carrying out the pH adjustment, can not obtain the primary particle of the titanium dioxide fine particles that quilt is generated between processing is with face or accelerate crystallization speed or crystallization control type under the state of aggregation.

In addition, at above-mentioned fluidic at least one, for while crystallization control type and crystallization degree can add hydrogen peroxide.Thus, for crystallization and noncrystalline, in addition for anatase octahedrite, the plate titanium, the crystal type of rutile etc. has the advantage of easy control, particularly when obtaining crystal type and be the titanium oxide ultra micron of rutile-type, the interpolation of this hydrogen peroxide is effective.

In addition,, so adding under the situation of hydrogen peroxide except above-mentioned, owing to can under the lower temperature about 40 ℃, carry out crystallization, so fluidic temperature treatment ratio is easier to.

In addition, the alkaline aqueous solution of adjusting in the agent with above-mentioned pH cooperates, and can add being selected from terepthaloyl moietie, Ucar 35, trimethylene, 1; The 2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 2; The 3-butyleneglycol, 1,5-pentanediol, 2-butylene-1,4-glycol, pinakon; Ethohexadiol, glycerine, at least a in the hexane diol, and 1,2, divalent alcohol in the 6-hexane trivalent alcohol or trivalent alcohol.

As the effect in the titanium dioxide ultra micron of this dihydroxylic alcohols or trihydroxylic alcohol is manufactured, can enumerate the chemisorption of the titanium oxide examined by formation to single (special face), hinder certain growth of single, obtain single shape and crystal type thus.For example, just obtaining under the high crystalline titanium oxide ultra micron situation of Detitanium-ore-type easily.In addition, the interpolation of this divalent alcohol or trivalent alcohol produces effect in the situation that is purpose through the dispersed high state of its finishing maintenance is inferior.

In addition, at above-mentioned fluidic at least one, can add and dissolve the glass that contains silicon oxide and/or silicon at least in hydrochloric acid, sulfuric acid and nitric acid a kind and contained at least a mixture of the material in the Si composite oxide and/or the material that soluble solids forms of containing.Thus, contain silicon oxide or monox composite oxides, the titanium oxide compound with photocatalyst performance is separated out in TiO 2 particles inside, very convenient under the situation of the such titanium oxide compound of needs.

In addition, at above-mentioned fluidic at least one, add after the acid of the cl ions that contains hydrochloric acid etc., can and then add the Bu Langsi Taide alkali of at least a kind of nitrate ion and phosphate ion etc.What explain is this moment, as titanium compound, uses the titanium tetrachloride that is generated hydrogenchloride by hydrolysis, preferred for the addition that reduces hydrochloric acid.The interpolation of such acid, very convenient under the situation of the titanium oxide that for example generates plate titanium type.What explain is, adds the fluid of above-mentioned cloth Lanace Taide alkali, can be the fluid that has added above-mentioned acid, also can be the expection different fluids.

In addition; At above-mentioned fluidic at least one; Can add, be the oxide compound of representative and contain aluminium, zirconium, silicon with aluminum oxide, zirconium white, silicon oxide, weisspiessglanz, White tin oxide, zinc oxide; At least a metallo-chelate in antimony, tin, zinc, the titanium, the organometallic compound that annular metal oligopolymer or metal alcoholate are such.Through the ultramicronized surface of titanium oxide being used the coating that forms by above-mentioned substance cover the photocatalyst activity of this particle of may command.Here, though think that the titanium oxide of rutile-type compares with the titanium oxide of Detitanium-ore-type and do not have photocatalyst activity, in fact has photocatalyst activity.Owing to so can fully control the photocatalyst activity of the titanium oxide of rutile-type, contain under the situation of titanium oxide ultra micron and organometallic compound that useful oxide compound carried out the surface-treated rutile-type very convenient.Certainly, to the titanium oxide of other crystal type, this is surface-coated also to be effective.

Like this; Through utilizing the surface-coated of oxide compound, organometallic compound; Can control the ultramicronized photocatalyst activity of titanium oxide fully, therefore at liquid-crystal display (LCD), plasma display (PDP); Under the situation about using in the antireflection film of the display surface of the flat-panel monitor (FPD) of electroluminescent display (EL) etc. etc., can utilize this effect especially.

In addition, at least one, can add the cinnamic verivate of vinylbenzene, chloro-styrene and vinyl toluene etc. at above-mentioned fluidic; Vinylformic acid, and acrylic acid verivate of methyl acrylate etc.; Polymerizable monomer, the carboxyl of the verivate of the methylacrylic acid of methylacrylic acid, TEB 3K etc. etc. or metal complex with organic cpds of nitrogenous base, calixarene (calixarene) compound, metalliferous dye, and nigrosine (nigrosine) etc. is not the antistatic agent of resin; The multipolymer that contains quaternary ammonium group or quaternary ammonium hydroxide contains the multipolymer of sulfonic group or sulphonate-base, contains the antistatic agent of anti-electrostatic resin etc. of the multipolymer etc. of carboxylic acid group or carboxylate group.Through adding polymerizable monomer since can be in polymerizable monomer homodisperse, dissolving titanium oxide ultra micron and antistatic agent, therefore convenient.In addition, the interpolation of antistatic agent is being made in order to be Electronic Paper, and electrophotography shows the shadow agent, and spacer for liquid crystal display apparatus is very convenient under the ultramicronized situation of titanium oxide that the purposes of photochromic particle etc. is utilized.

In addition,, also can contain lime carbonate different and phosphoric acid or hydroxylapatite and implement at least one at above-mentioned fluidic with above-mentioned titanium compound.For it, very convenient under the situation of the TiO 2 porous body that disposes on the skeleton surface that is produced on the porous insert that forms by titanium oxide phosphatic rock complex body or calcium phosphate.

TiO 2 porous body so for example, can be removed decomposing, and it is smelly to disappear, antibiotic, antifouling, the effect activation of antifog grade.Therefore, can be at coating, fibre product, unhealthy buildings (sick house) agent for releasing; Building materials, the interior material of automobile etc., furniture, tame electrical article; Residential equipment, tableware etc. antifouling, it is smelly to disappear, degerming; Or the innocent treatment agent of industrial water drainage exhaust etc. preferably uses in the various purposes such as medical material.

And, in order to promote the coordination of organic ligand, or carry out the promotion of crystallization, or the change of crystal type etc., can be with handling with heating (heating) between face, maybe can be between handling with face irradiation ultraviolet radiation (UV), or can between processing is with face, supply with ultrasonic energy in addition.Particularly, handle to handle being provided with under the situation of temperature head the 1st, owing to can in the film fluid, convection current taking place, so have and to promote thus to react and the advantage of above-mentioned purpose with face 2 with face 1 and the 2nd.

More specifically,, for example, with at least one side of portion 10,20 well heater or the big envelope through thermal medium are set, can heat (heating) film fluid through reason throughout for heating (heating).In addition, for irradiation ultraviolet radiation (UV), for example reason is provided with the element of the lamp etc. of irradiation ultraviolet radiation with at least one side of portion 10,20 throughout, can be from corresponding processing with facing film fluid irradiation ultraviolet radiation (UV).In addition, for supplying with ultrasonic energy, at least one side that for example can manage throughout with portion 10,20 is provided with ultrasonic oscillator.

Like this, can be manufactured on and be dispersed with volume average particle size 0.5～1000nm, preferred 1～30nm, the more preferably ultramicronized dispersion liquid of the titanium oxide of 1～10nm (suspension-s) in the solvent.And; At the aqueous solution that has dissolved titanium compound or be used for making its hydrolysis the water system solvent any one has added under the situation of above-mentioned dispersion agent at least; Can make from the teeth outwards dispersion agent by coordinate titanium oxide ultra micron by dispersed dispersion liquid (suspension-s), the ultramicronized redispersibility of the titanium oxide that obtains becomes very good.

As stated, remove the 1st d1 of importing portion, beyond the 2nd d2 of importing portion; The 3rd d3 of importing portion also can be set on treatment unit, under this situation, for example can be from each importing portion; PH is adjusted agent, contain the solution of at least a titanium compound, dispersion agent imports in the treatment unit respectively.Like this, but each manages concentration, the pressure of each solution, can more critically control the reaction that the titanium oxide ultra micron generates.Even under the situation that is provided with the importing portion more than the 4th, the fluid sectionalization that equally also can be so will import to treatment unit.

In addition; In the present invention; Can be near discretely each other in the ultramicronized method of manufacture of titanium oxide in the film fluid that forms between with face of subtend processing that set, that at least one direction is rotated for the opposing party under the situation of use reversed micelle method; Also with above-mentioned situation under substantially identical, for example, at suitable organic solvent (for example; Octane-iso) (for example two (2-ethylhexyl) sodium sulfonates (AOT) or T 46155 (20) sorbitan oleic acid ester (Port リ オ キ シ エ チ レ Application (20) ソ Le PVC タ Application オ レ one ト) are made reversed micelle solution to add entry and suitable dispersion agent in.Secondly contain the solution of four titanium butoxide (TNBT) that useful 1-butanols is diluted to normality as 2 fluids through use, can obtain containing the ultramicronized dispersion-s of titanium oxide.

Below, describe in more detail for disclosed embodiment of the present invention.But the present invention has more than and is defined in these embodiment.

What explain is; In following embodiment; So-called " from central authorities "; Refer to such an extent that be the meaning of " from the 1st d1 of importing portion " of treatment unit shown in above-mentioned, Fig. 1 (A), the 1st fluid is meant that the above-mentioned the 1st is processed liquid, that the 2nd fluid is meant is above-mentioned, treatment unit shown in Fig. 1 (A) " that import from the 2nd d2 of importing portion, above-mentioned the 2nd is processed liquid.

(embodiment H1)

Use as Fig. 1 (A) shown in, can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with the device that evenly mixes reaction in the film fluid of face 1, formation between 2, on one side with the reaction that is hydrolyzed of titanium tetrachloride solution one side uniform mixing in above-mentioned film fluid.

To be adjusted to the aqueous solution of pH2 on one side as the 1st fluidic with aqueous hydrochloric acid from central authorities; Carry out liquor charging for 95 ℃ with supply pressure/back pressure=0.20MPa/0.01MPa, rotating speed 1000rpm, liquor charging temperature; To import processing with face 1, between 2 with 3ml/min as the 2nd fluidic titanium tetrachloride aqueous solution (Ti content is 15.4 quality %) on one side.Titanium oxide ultra micron dispersion liquid is discharged from face from handling.In addition, the temperature of liquid effluent also is 95 ℃.In order to remove the residual chlorine that dereaction generates, with the electric dialysis apparatus G3 type of Asahi Chemical Industry's industry (strain) system, Yi Bian keep watch on the pH of dispersion liquid, Yi Bian the electric dialysis of the titanium oxide ultra micron dispersion liquid that enforcement obtains obtains titanium oxide ultra micron dispersion liquid.

The titanium oxide ultra micron dispersion liquid that obtains is made its drying and obtains titanium dioxide powder with 120 ℃ of moisture eliminators.The ultramicronized crystallization of the titanium oxide that obtains like this is than implementing with following method.

(crystallization ratio)

X-ray diffraction is measured with panalytical powder process end X-ray diffraction device.Crystallization is obtained than resolving software through accessory Rietveld in the device, is 98.2% rutile titanium dioxide.

(primary particle size)

Titanium oxide ultra micron dispersion liquid is made its drying on the sample bench of electroconductibility, use scanning electron microscope, observe, measured the particle size range in whole visual field with the multiplying power more than 100,000 times.Primary particle size is 10～15nm.Particle is shaped as sphere in addition.

(redispersibility)

The titanium oxide ultra micron powder that obtains is cooperated so that form 10w/w% titanium oxide/1w/w% Vinylpyrrolidone polymer aqueous dispersions; With high-speed stirring type dispersion machine (trade(brand)name: ClearMix; M technology society system) stir, the result obtains titanium oxide ultra micron dispersion liquid once more.This titanium oxide ultra micron powder is made its drying and obtains titanium oxide ultra micron powder once more with 120 ℃ of moisture eliminators.Use scanning electron microscope, observe, measured the particle size range in a visual field with multiplying power more than 100,000 times.Primary particle size is 10～15nm.The redispersibility of confirming as the titanium oxide ultra micron powder that obtains is good.

(embodiment H2)

Except that becoming rotating speed the 2000rpm, other and embodiment H1 obtain titanium oxide ultra micron powder equally.

(embodiment H3)

Except that becoming rotating speed the 3000rpm, other and embodiment H1 obtain titanium oxide ultra micron powder equally.

(embodiment H4)

Except that becoming supply pressure the 0.10MPa, other and embodiment H1 obtain titanium oxide ultra micron powder equally.

(embodiment H5)

Except that becoming supply pressure the 0.30MPa, other and embodiment H1 obtain titanium oxide ultra micron powder equally.

(embodiment H6)

Except that becoming back pressure the 0.10MPa, other and embodiment H1 obtain titanium oxide ultra micron powder equally.

(Comparative Example H 1)

To be adjusted to the aqueous solution 200g of pH2 on one side with aqueous hydrochloric acid, in beaker, with the condition stirring of 95 ℃ of solution temperatures, 140rpm, Yi Bian drop into titanium tetrachloride aqueous solution (Ti content is 15.4 quality %) solution 20g.To obtain water-dispersion titanium oxide with the same method of the foregoing description.

(embodiment H7)

To be modulated into the aqueous solution of pH 1 on one side as the 1st fluidic with aqueous hydrochloric acid from central authorities; Carry out liquor charging for 95 ℃ with supply pressure/back pressure=0.30MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature; To import processing with face 1, between 2 with 4ml/min as the 2nd fluidic tetraisopropoxy titanium (WAKO one-level) on one side.The water-dispersion titanium oxide dispersion is discharged from face from handling.

(primary particle size)

Titanium oxide ultra micron dispersion liquid is made its drying on the sample bench of electroconductibility, use scanning electron microscope, observe, measured the particle size range in a visual field with the multiplying power more than 100,000 times.Primary particle size is 10～20nm.Particle is shaped as sphere in addition.

(redispersibility)

The titanium oxide ultra micron dispersion liquid powder that obtains is cooperated so that form 10w/w% titanium oxide/1w/w% Vinylpyrrolidone polymer aqueous dispersions; With high-speed stirring type dispersion machine (trade(brand)name: ClearMix; M technology society system) stir, the result obtains titanium oxide ultra micron dispersion liquid once more.This titanium oxide ultra micron dispersion liquid is made its drying with 120 ℃ of moisture eliminators, obtain titanium oxide ultra micron powder once more.Use scanning electron microscope, observe, measured the particle size range in a visual field with multiplying power more than 100,000 times.Primary particle size is 10～20nm.The redispersibility of confirming as the titanium oxide ultra micron powder that obtains is good.

(embodiment H8)

Except that becoming rotating speed the 2000rpm, other and embodiment H7 obtain titanium oxide ultra micron dispersion liquid equally.

(embodiment H9)

Except that becoming rotating speed the 3000rpm, other and embodiment H7 obtain titanium oxide ultra micron dispersion liquid equally.

(embodiment H10)

Except that becoming 0.10MPa to supply pressure, other and embodiment H7 obtain titanium oxide ultra micron dispersion liquid equally.

(Comparative Example H 2)

To be adjusted to the aqueous solution 200g of pH 1 on one side with aqueous hydrochloric acid, in beaker, stir with 95 ℃ of solution temperatures, 140rpm, Yi Bian drop into tetraisopropoxy titanium (WAKO one-level) 20g.To obtain titanium oxide ultra micron dispersion liquid with the same method of the foregoing description.

The above results is shown in table 16.What explain is that embodiment 1～10 in the table and comparative example 1～2 are represented the foregoing description H1～H10 and Comparative Example H 1～H2 respectively.

[table 16]

(I) fine magnetic-substance particle

Below, the reaction of generation fine magnetic-substance particle of the present invention is described.

This reaction, use device as Fig. 1 (A) shown in, can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, between 2, on one side one side uniform mixing takes place by the strong hand.

At first; From the 1st d1 of importing portion as 1 stream; The fluid that will contain at least a magnetic substance raw material; Importing can be near each other the subtend configuration, that at least one side is rotated with respect to the opposing party processing discretely with 1,2 in face, the film fluid that generation is made up of the 1st fluid between this processing is with face.

Then,, will contain the fluid of the fine magnetic-substance particle precipitation agent of at least a reductive agent etc., directly import the above-mentioned film fluid that constitutes by the 1st fluid as the 2nd fluidic from the 2nd d2 of importing portion as other stream.

As stated, the pressure equilibrium of applied pressure and will be between the processing of supply with pressing and being rotated through fluidic is with face apart from the processing of having controlled with face 1, can form the film fluid between 2.And the 1st fluid and the 2nd fluid interflow in this film fluid and mixed can make fine magnetic-substance particle separate out and generates the reaction of fine magnetic-substance particle.From reaction treating device, be removed as the magnetic fluid that contains fine magnetic-substance particle.

What explain is, owing to can carry out above-mentioned reaction with face 1, between 2 and get final product handling, therefore, also can import the 2nd fluid from the 1st d1 of importing portion on the contrary with above-mentioned, imports the 1st fluid from the 2nd d2 of importing portion.That is, the appellation of the what is called the 1st, the 2nd in each fluid is that the fluidic n of a plurality of existence of expression is individual, and just also can there be the fluid more than the 3rd in the mark in order to discern.

The particle diameter of the fine magnetic-substance particle that obtains, single dispersity, the control of crystal type in addition can be through change handling with the rotating speed of face 1,2 or processing with face 1, distance and film flow rate of fluid or temperature between 2, and perhaps material concentration etc. is regulated.

In addition; In the present invention; Use add in organic solvent that dispersion agent closes the magnetic substance aqueous solution of raw material and the 1st reversed micelle solution that obtains as above-mentioned the 1st fluid and use contain at least a fine magnetic-substance particle precipitation agent the 2nd reversed micelle solution as above-mentioned the 2nd fluidic situation under; That is, use under the situation of reversed micelle method, also can make magnetic fluid and fine magnetic-substance particle in method as the synthesizing magnetic body.

As the metal that contains in the fine magnetic-substance particle that obtains with method of manufacture of the present invention,, just it is not done special the qualification, but preferably contain nickel, cobalt as long as have magnetic with the state of monomer or compound; Iridium, iron, platinum, gold, silver; Manganese, chromium, palladium, yttrium; In the transition element of lanthanon (neodymium, samarium, gadolinium, terbium) etc. at least a kind.

In the fine magnetic-substance particle, also can contain above-mentioned element in addition.For example, copper, zinc, magnesium, rhenium, bismuth, silicon.

What explain is, above-mentioned fine magnetic-substance particle also can have rerum natura beyond the magnetic, jointly for example as semi-conductive rerum natura.For example, by the Tc EuX also lower (X representes S, the VI family element of Se etc.), CdCr than 150k ₂Se ₄The magneticsemiconductor particulate that forms.

In addition; The magneticsemiconductor particulate that is formed by alloy semiconductor is arranged; Said alloy semiconductor forms as follows: in II-VI compound semiconductor, III-V compound semiconductor, IV compound semiconductor, I-III-VI compound semiconductor, the 3d transition metal of Mn etc. is sneaked into as magnetic element.In this example,, CdMnTe is arranged, CdHgMnTe as the representational II-VI DMS of family (thin magneticsemiconductor).And, as the representational III-V DMS of family, InMnAs (50k) is arranged, GaMnAs (160k), InGaMnAs (130k).What explain is, the magnetic transition temperature of expressing strong of the numerical tabular in above-mentioned (), and above-mentioned each material is for to show ferromagnetic material at low temperature.

As other material, the fine magnetic-substance particle that is formed by BeMnZnSe is arranged.

On the other hand, particularly, also can be material with above-mentioned rerum natura.Iron-copper for example, ferroplatinum, nickel, Rhometal, cobalt, ferro-cobalt, manganese, manganeseirom, titanium, ferro-titanium, vanadium, vanadium copper alloy, magnet (Fe ₃O ₄), as starting material itself, for not having magnetic substance as semi-conductive rerum natura.

But; Even have single rerum natura as stated for starting material unit; Be added under the situation in the particulate that forms by single starting material with above-mentioned inhomogeneous starting material; Or form under the situation of the multiple aggregate of having gathered at the particulate that forms by single starting material, have from each raw-material multiple rerum natura.Therefore in this application, in the goods that contain fine magnetic-substance particle at least, in a plurality of rerum naturas that these goods had, the material that utilizes magnetic is treated as magnetic-substance.For example, even have jointly, with utilizing goods as the rerum natura of magnetic substance specially as magnetic-substance as the rerum natura of magnetic substance with as the aggregate of semi-conductive rerum natura.

Instance as this magnetic-substance; Can enumerate having fixed the material (permanet magnet) that state utilizes as all magnetic poles of goods; Be utilized in goods all in the material (magnetic is given medicament etc. for the magnetic core of electromagnet, magnetic substance conjugated polymer system agglutinant) of the phenomenon changed of magnetic pole; Utilize the material (magnetic recording medias of disk etc.) of the magnetic pole conversion of part in the goods, the material (electromagnetic shielding material etc.) that carries out the blocking in magnetic field.In addition, magnetic-substance is not limited to the solid-like material, and goods of powder (printing press is with toning agent etc.) or liquid goods (magnetic fluid) also are a kind of of this magnetic-substance.

As the method for manufacture of these magnetic substance products, available various method for example, can be made: solidify particulate or other starting material of the majority that contains fine magnetic-substance particle, be configured as different shape as follows; Or in resin etc., sneak into the particulate of the majority that contains fine magnetic-substance particle; Or on the surface of dish etc., adhere to the particulate of the majority that contains fine magnetic-substance particle with the means of coating, vapor deposition, sputter etc.And, can in fluid, will contain fine magnetic-substance particle majority the particulate colloidal dispersion and make.

In the present invention; Can near separate each other subtend processing that set, that at least one side is rotated with respect to the opposing party obtain under the situation of fine magnetic-substance particle in the formed film fluid between with face; For example; In the situation of making by the such fine magnetic-substance particle that forms by metal of FeCu (iron-copper) particulate, at first, can through use in the water system solvent, dissolved as molysite for example iron protochloride, as the aqueous solution of the copper sulfate of mantoquita etc. as the 1st fluid; Use has been dissolved the aqueous solution as the fine magnetic-substance particle precipitation agent of the reductive agent of hydrazine or dimethylaminoethanol etc. as the 2nd fluid, makes the iron-copper particulate.As above-mentioned water system solvent, do not do special qualification in addition, can use the Purified Water of ion exchanged water or pure water etc.

The reductive agent that uses as the fine magnetic-substance particle precipitation agent is not done special qualification, for example, can enumerate Peng Qinghuana, inferior sodium phosphate, hydrazine; The ion of transition metal (tervalent titanium ion, the cobalt ion of divalence etc.), methyl alcohol, ethanol, the alcohol of 2-propyl alcohol etc.; Or xitix, in addition can enumerate terepthaloyl moietie, gsh, organic acid (Hydrocerol A, oxysuccinic acid; Tartrate etc.), reductibility carbohydrate (glucose, semi-lactosi, seminose, fructose; Sucrose, SANMALT-S, raffinose, stachyose etc.), and glycitols or Sorbitol Powder etc.In addition, also can use amine as reductive agent, as related amine, but propylamine for example, butylamine, hexylamine, diethylamine, dipropyl amine, dimethylethyl amine; The diethylammonium methylamine, triethylamine, quadrol, N,N,N, 1,3-diaminopropanes; N, N, N ', N '-tetramethyl--1,3-diaminopropanes, Triethylenetetramine (TETA), the fatty amine of TEPN etc., piperidines; The N-methyl piperidine, piperazine, N, N '-lupetazin, tetramethyleneimine, N-crassitude, the ester ring type amine of morpholine etc., aniline; Methylphenylamine, N, accelerine, Tolylamine, methyl oxyaniline, the aromatic amine of phenetidine etc., benzylamine, N-methylbenzylamine; N, N-dimethyl benzylamine, phenylethylamine, benzene dimethylamine, N, N, N ', the aralkylamine of N '-tetramethyl-benzene n n dimetylaniline etc. etc.In addition, as above-mentioned amine, for example also can enumerate methylamino ethanol, dimethylaminoethanol, trolamine; Thanomin, diethylolamine, methyldiethanolamine, Propanolamine; 2-(3-amino propyl amino) ethanol, butanolamine, hexanol amine, the alkanolamine of dimethylamino propyl alcohol etc.

In above-mentioned reaction, for the nitrogenize fine magnetic-substance particle also can be between handling with face the mixed gas of importing nitrogenous gas or nitrogen and hydrogen, or ammonia.Equally, in fine magnetic-substance particle, form under the situation of oxide scale film, can be between handling with face the oxygen of the suitable oxygen concn of importing and the mixed gas of rare gas element implement.And, handle in order to promote each, can heat (heating) and handle with irradiation ultraviolet radiation (UV) between face or between handling or between processing is with face, give ultrasonic energy and implement with face.

In addition, making by magnet (Fe ₃O ₄) under the situation of the fine magnetic-substance particle that forms of the such MOX of particulate; For example; Through with the following aqueous solution as the 1st fluid: in the water system solvent, will use iron protochloride or Iron nitrate or ferrous sulfate, use dissolvings such as iron(ic)chloride as 3 valency iron ion salt: the aqueous solution of 3 valencys=1: 2 so that divalent iron ion and 3 valency iron ions are divalent as divalent iron ion salt; Use and dissolved in the 2nd fluid, can make the magnet particulate as the alkalescence of sodium hydroxide or Pottasium Hydroxide or ammonia etc. the aqueous solution of the fine magnetic-substance particle precipitation agent of heavy agent altogether.As above-mentioned water system solvent, do not do special qualification in addition, can use the Purified Water of ion exchanged water and pure water etc.The water-soluble organic solvent that also can mix in addition, methyl alcohol etc. with various purpose.

In addition; Under the situation of making the fine magnetic-substance particle that forms by metallic sulfide; For example; Through use in the water system solvent, dissolved as the nitrate salt of the cobalt of magnetic substance and in addition as the aqueous solution of the nitrate salt of the copper of other metal etc. as above-mentioned the 1st fluid, use and in the 2nd fluid, dissolved sodium sulphite (Na ₂S) aqueous solution or the hydrogen sulfide (H in such sulphur (S) source ₂S) sulphur of such gas (S) source can make this fine magnetic-substance particle as the fine magnetic-substance particle precipitation agent.These also with above-mentioned same, can carry out nitriding treatment or oxide treatment according to purpose, heat treated or UV processing etc.

In addition, at least a fluid in above-mentioned fluid, can be added on coordinate dispersion agent on the surface of fine magnetic-substance particle.As dispersion agent, do not do special qualification, solution there is good solubility, can the fine magnetic-substance particle of separating out various dispersion agents of dispersive well in solution all can be used simultaneously.Particularly, preferably use macromolecule dispersing agent.As above-mentioned macromolecule dispersing agent, can use various materials, for example; Can enumerate polymine, the macromolecule dispersing agent of Vinylpyrrolidone polymer etc., ROHM; The macromolecule dispersing agent that has carboxylic acid group's hydro carbons in the molecule of CMC 99.5 etc.; Poval (Z 150PH), or, the macromolecule dispersing agent with polar group of the multipolymer etc. of polyethyleneimine: amine moiety and polyethylene oxide part is arranged in 1 molecule.In addition, its molecular weight is preferably below 100000.In addition, also can use commercially available dispersion agent.As above-mentioned commercially available article, for example can enumerate Solsperse 20000, Solsperse24000, Solsperse 26000, and Solsperse 27000, Sols perse 28000, Solsperse 41090 (above, Avecia society system); Disperbyk 160, Disperbyk161, and Disperbyk 162, and Disperbyk 163; Disperbyk 166, and Disperbyk 170, and Disperbyk 180, and Disperbyk 181; Disperbyk 182, and Disperbyk 183, and Disperbyk 184, and Disperbyk 190; Disperbyk 191, and Disperbyk 192, and Disperbyk 2000, Disperbyk 2001 (above, BYK Chemie society system); Polymer100, Polymer 120, and Polymer 150, and Polymer 400, and Polymer 401; Polymer402, Polymer 403, and Polymer 450, and Polymer 451, and Polymer 452; Polymer453, EFKA-46, EFKA-47, EFKA-48, EFKA-49; EFKA-1501, EFKA-1502, EFKA-4540, EFKA-4550 (above, EFKA Chemical society system); FLOWLEN DOPA-158, FLOWLEN DOPA-22, FLOWLEN DOPA-17, FLOWLEN G-700, FLOWLEN TG-720W, FLOWLEN-730W, FLOWLEN-740W, FLOWLEN-745W (above, common prosperity society chemistry system); AJISPER PA111, AJISPER PB711, AJISPER PB811, AJISPER PB821, AJISPER PW911 (above, aginomoto society system); JONCRYL 678, and JONCRYL 679, JONCRYL 62 (above, Johnson Polymer society system) etc.These dispersion agents can use separately, also can more than 2 kinds and use.Can use following material to implement: oleic acid and erucic acid, linolic acid, six phosphoric acid, eight phosphoric acid, four phosphoric acid; The Tripyrophosphoric acid class of triphosphoric acid etc., acetate, the polymeric organic acid or the Vinylpyrrolidone polymer of acrylic or methacrylic acid etc., the macromolecule organic that Z 150PH or sodium hexametaphosphate are such; 2 mercapto ethanol, Thiovanic acid, 2-mercaptoethylamine, β-thiodiglycol; 2,2 '-thio-alcohol of thiodiglycolic acid etc., or PS, or phosphinoxides.

The pH that can add aptly in addition for the pH value of adjusting when reaction adjusts agent.Under the situation of reaction conditions as alkalescence,, can use aqueous sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide aqueous solution, baryta water, the strong basicity of ammoniacal liquor etc. or the weakly alkaline aqueous solution as pH adjustment agent.

Reaction conditions as pH adjustment agent, can use aqueous hydrochloric acid or aqueous nitric acid, the strongly-acid or the weakly acidic aqueous solution of acetic acid aqueous solution or aqueous citric acid solution etc. as under the tart situation.

And, can heat (heating) and handle with irradiation ultraviolet radiation (UV) between face or between handling or between processing is with face, give ultrasonic energy with face.Particularly, be provided with under the situation of temperature head with face 2 with face 1 and the 2nd processing,, therefore have to have thus to make and react promoted advantage owing to can in the film fluid, convection current take place in the 1st processing.

More specifically,, for example with at least one side of portion 10,20 well heater or the big envelope through thermal medium are set, can heat (heating) film fluid through reason throughout for heating (heating).In addition, for irradiation ultraviolet radiation (UV), for example reason is provided with the element of the lamp etc. of irradiation ultraviolet radiation with at least one side of portion 10,20 throughout, can be from corresponding processing with facing film fluid irradiation ultraviolet radiation (UV).In addition, for supplying with ultrasonic energy, at least one side that for example can manage throughout with portion 10,20 is provided with ultrasonic oscillator.

And; Through can guarantee to reduce pressure or the container of vacuum state in carry out above-mentionedly separating out, handling at least 2 sides that the back fluid is discharged from and become decompression or form vacuum state; The degassing of contained gas in gas that carries out in evolution reaction, producing and the above-mentioned fluid, or above-mentioned fluidic desolventizing.Thus; Even with almost carrying out simultaneously of separating out of the fine magnetic-substance particle situation that desolventizing handles under; Be discharged from atomize with face from handling because contain the fluid of the fine magnetic-substance particle of between handling, separating out with face, so this fluidic surface-area increase, desolventizing efficient is very high.Therefore than till now also simply, 1 operation is carried out fine magnetic-substance particle and is made and handle and the desolventizing processing in fact.

Like this, can be manufactured on and disperseed volume average particle size 0.5～1000nm, preferred 1～30nm, the more preferably magnetic fluid of the water system dispersion-s (suspension-s) of the fine magnetic-substance particle of 5～11nm in the water system solvent.And; In the aqueous solution of the nitrate salt that has dissolved metal etc., add under the situation of dispersion agent; Can make the surface go up dispersion agent by coordination fine magnetic-substance particle be magnetic fluid by dispersed aqueous dispersion (suspension-s), the redispersibility of the fine magnetic-substance particle that obtains is good.Therefore also convenient under the situation of modulating once more according to the magnetic fluid of purpose.

As stated, remove the 1st d1 of importing portion, beyond the 2nd d2 of importing portion, the 3rd d3 of importing portion can be set on treatment unit also; Under this situation, for example can pH be adjusted agent from each importing portion; The aqueous solution of metals ion, dispersion agent, the fine magnetic-substance particle precipitation agent imports in the treatment unit respectively.Like this, but each manages concentration, the pressure of each solution, can more critically control the reaction that fine magnetic-substance particle generates.Even under the situation that is provided with the importing portion more than the 4th, the fluid sectionalization that equally also can be so will import to treatment unit.

In addition; In the present invention; Can be near each other using under the situation of reversed micelle method in the method for manufacture of the fine magnetic-substance particle in the film fluid that forms between with face of subtend processing that set, that at least one direction is rotated for the opposing party discretely, also with above-mentioned situation under cardinal principle identical, for example; Under the situation of making the ferroplatinum particulate; At suitable organic solvent for example in the heptane, in the ether of the alkane of the carbon number 7～12 of octane, nonane etc. or Anaesthetie Ether and dipropyl ether etc., add entry and suitable dispersion agent for example cetyl trimethylammonium bromide (CTAB) or penta methylene glycol lauryl ether, make reversed micelle solution.In this reversed micelle solution, add the nitrate salt or the vitriol of iron and platinum, hydrochloride, the aqueous solution of the iron of acetate or metal carbonyl etc. or the compound of platinum is made the reversed micelle solution that contains iron and platinic compound as the 1st fluidic.Secondly through use contain the fine magnetic-substance particle precipitation agent be the reversed micelle solution of reductive agent as the 2nd fluid, can obtain containing the dispersion liquid of ferroplatinum particulate thus.

Below, describe in more detail for disclosed embodiment of the present invention.But the present invention has more than and is defined in these embodiment.

Use shown in Fig. 1 (A), can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, the reaction unit that evenly mixes in the formed film fluid between 2; Following mixed aqueous solution is reduced in above-mentioned film fluid, on one side uniform mixing obtain fine magnetic-substance particle on one side.

What explain is; In following embodiment; So-called " from central authorities "; Refer to such an extent that be the meaning of " from the 1st d1 of importing portion " of treatment unit shown in above-mentioned, Fig. 1 (A), the 1st fluid is meant that the above-mentioned the 1st is processed liquid, that the 2nd fluid is meant is above-mentioned, treatment unit shown in Fig. 1 (A) " that import from the 2nd d2 of importing portion, above-mentioned the 2nd is processed liquid.

(example I 1)

On one side will be as the 1st fluidic 10% hydrazine aqueous solution from central authorities; Carry out liquor charging for 80 ℃ with supply pressure/back pressure=0.02MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature; To just use on one side ammoniacal liquor modulation pH be 20% ferrous sulfate/18% copper sulfate/2%BYK-190 (BYKChemie society system) aqueous solution of 12 as the 2nd fluid, import with 10ml/min and to handle with face 1, between 2.As the magnetic fluid of the iron-copper particle dispersion liquid of water system from handling with between face 1, be discharged between 2.

Secondly,, use dialysis tubing to remove impurity, use transmission electron microscope (TEM), observed the iron-copper particulate in this dispersion liquid for the iron-copper particle dispersion liquid that obtains.From wherein selecting 100 particles arbitrarily, measure average primary particle diameter, the result is 9.3nm.And, iron ion and cupric ion to cooperate ratio (atomicity than) be 10: 9.And the yield of this iron-copper particulate is 94%.In addition, the iron-copper particulate that obtains is confirmed that particle is shaped as sphere as a result through the transmission-type microscope.

(example I 2)

On one side will be as the 1st fluidic 0.3mol/L caustic soda (sodium hydroxide) aqueous solution from central authorities; Carry out liquor charging for 95 ℃ with supply pressure/back pressure=0.40MPa/0.01MPa, rotating speed 500rpm, liquor charging temperature; On one side will be as the 2nd fluidic, use ferric chloride hexahydrate as feed metal salt, cobalt chloride hexahydrate, nickel chloride hexahydrate, and chromium chloride hexahydrate, with the Fe of 0.25mol/L ³⁺The Co of the aqueous solution, 0.10mol/L ²⁺The Ni of the aqueous solution, 0.10mol/L ²⁺The aqueous solution, and the Cr of 0.10mol/L ³⁺The aqueous solution mixes so that form Fe ³⁺: Co ²⁺: Ni ²⁺: Cr ³⁺=2: 1: 0.3: 0.3 solution imports processing with face 1, between 2 with 10ml/min.As the magnetic fluid of black particle dispersion liquid from handling with being discharged between face.

The throw out that obtains the part of the black particle dispersion liquid that obtains is filtered carries out ultimate analysis, and Fe is 47.6% as a result, and Co is 14.1%, and Ni is 2.9%.Cr is 2.4%.Use has been used the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of laser Doppler method and has been measured size-grade distribution, and volume average particle size is 18nm as a result.This particulate is measured system (PPMS) with physical property and has been carried out magneticmeasurement, and saturation magnetization σ is 57.2 * 10 as a result ^-6Wbm/kg, confining force HcJ are 421kA/m.

And after this black particle dispersion liquid cleaned with pure water, vacuum-drying obtained the black particle powder.Put into this powder in the ion exchanged water once more; With high-speed stirring type dispersion machine (trade(brand)name: ClearMix; M technology society system) stir, the result obtains black particle dispersion liquid once more, and is identical before volume average particle size and the vacuum-drying; Volume average particle size is 18nm, and the redispersibility of confirming as the black particle powder that obtains is good.

(example I 3)

To water, (deoxidation: below the 0.1mg/L) dissolve NaBH from central authorities on one side ₄The reductive agent aqueous solution in add, mixed alkane solution and the reversed micelle solution (0.9%NaBH that obtains of dioctylis sulfosuccinas natricus and decane and oily enamine 2ml ₄/ 18.8% de-oxygenised water/12.7% dioctylis sulfosuccinas natricus/oily enamine of 65.9% decane/1.7%), carries out liquor charging for 50 ℃ with supply pressure/back pressure=0.10MPa/0.01Mpa, rotating speed 1000rpm, liquor charging temperature as the 1st fluid; To in water, (deoxidation) three oxalic acid, three ammonium iron (Fe (NH have been dissolved on one side ₄) ₃(C ₂O ₄) ₃) and chlorination potassium platinate (K ₂PtCl ₄) aqueous metal salt in add, mixed dioctylis sulfosuccinas natricus and decane alkane solution and be modulated into reversed micelle solution (1.1%Fe (NH ₄) ₃(C ₂O ₄) ₃/ 0.9%K ₂PtCl ₄The solution of/18.9% de-oxygenised water/12.8% dioctylis sulfosuccinas natricus/66.3% decane imports processing with face 1, between 2 with 10ml/min.Magnetic fluid as the reversed micelle solution that contains particle dispersion liquid is discharged from face from handling.

In order to destroy the reversed micelle that obtains, add water: the mixing solutions of methyl alcohol=1: 1 is separated into water and oil phase.The oil phase side obtain microparticulate state.With oil phase side water: the mixing solutions of methyl alcohol=3: 1 is cleaned 5 times.

, add methyl alcohol, make particulate take place to flocculate and make its sedimentation thereafter.Remove supernatant, add heptane and carry out redispersion.And the sedimentation and the sedimentation of heptane dispersive that utilize for 3 times methyl alcohol to add repeatedly disperse, and add heptane at last, and the mass ratio (water/tensio-active agent) of modulation water and tensio-active agent is 2 FePt (ferroplatinum) particle dispersion liquid.

For the ferroplatinum particle dispersion liquid that obtains, remove impurity with dialysis tubing, use transmission electron microscope (TEM) to observe the ferroplatinum particulate in this dispersion liquid.From wherein selecting 100 particles arbitrarily, measure average primary particle diameter, the result is 4.0nm.

(Comparative Example I 1)

On one side with high-speed stirring type dispersion machine (trade(brand)name: ClearMix; M technology society system) stirs 0.3mol/L caustic soda (sodium hydroxide) aqueous solution with 95 ℃ of liquid temperature, 20000rpm; Import on one side following solution: use ferric chloride hexahydrate as feed metal salt, cobalt chloride hexahydrate, nickel chloride hexahydrate, and chromium chloride hexahydrate, the Fe of mixing 0.25mol/L ³⁺The aqueous solution, the Co of 0.10mol/L ²⁺The aqueous solution, the Ni of 0.10mol/L ²⁺The aqueous solution, and the Cr of 0.10mol/L ³⁺The aqueous solution is so that Fe ³⁺: Co ²⁺: Ni ²⁺: Cr ³⁺=2: 1: 0.3: 0.3 solution.Obtain magnetic fluid as black particle dispersion liquid.

The particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) that laser Doppler method has been used in use is measured the size-grade distribution of the black particle dispersion liquid that obtains, and volume average particle size is 970nm as a result.

And; With the identical method of example I 2, the black particle powder that obtains is put in the ion exchanged water once more, with high-speed stirring type dispersion machine (trade(brand)name: ClearMix; M technology society system) stirs; The result obtains black particle dispersion liquid once more, and volume average particle size is also big before than vacuum-drying, and volume average particle size is 1640nm.

For obtaining fine magnetic-substance particle energy needed amount, compare with comparative example, though the volume average particle size of the foregoing description side diminishes, all be below 1/10th.The Energy efficiency of the method for manufacture of hence one can see that the foregoing description is excellent.

(J) biological uptake thing (dispersion)

Below, to describing for the operation that obtains biological uptake thing of the present invention through dispersion.

Particularly; Have the processing that can be rotated with respect to the opposing party with face and at least one side that subtend sets near isolating processing with face between; Disperse solvent as the 1st fluid (being processed liquid) water system; The oil-phase component that will contain fat-soluble pharmacological active substance is as the 2nd fluid (being processed liquid), and state feeds corresponding to each fluidic independent paths to keep independently with each fluid, imports to handle with between the face; Forming the film fluid, is the biological uptake thing through mixing the fine particle that each fluid obtains having desirable particle diameter therein.This biological uptake thing, as the dispersion liquid of the O/W shape that above-mentioned the 1st fluid is an external phase, above-mentioned the 2nd fluid exists as disperse phase in this external phase, from above-mentioned processing with being removed between the face.In addition, under the situation of using tensio-active agent, can in the 1st fluid or the 2nd fluid or each fluidic two sides, suitably add.

What explain is that said here pharmacological active substance is meant the material monomer and the compound that biology are shown physiological action or pharmacological action.For example, the meaning is meant pharmaceuticals quasi drug, the effective component that is contained in the food food additives protective foods makeup VITAMINs etc.

In addition; Have the processing that can be rotated with respect to the opposing party with face, at least one side that subtend sets near isolating processing with face between; Disperse solvent as the 1st fluid (being processed liquid) oil system, the water-phase component that will contain water miscible pharmacological active substance is as the 2nd fluid (being processed liquid), and state feeds corresponding to each fluidic independent paths to keep independently with each fluid; Import and handle with between the face; Form the film fluid, through mixing each fluid therein, the fine particle that obtains having desirable particle diameter is the biological uptake thing.This biological uptake thing is also with above-mentioned the same, as the dispersion liquid of the W/O shape that above-mentioned the 1st fluid is an external phase, above-mentioned the 2nd fluid exists as disperse phase in this external phase, from above-mentioned processing with being removed between the face.

Mix owing in each film fluid, carry out each fluidic as stated, therefore do not use uneven preparation to disperse modulator, can directly modulate, often produce uniform mixing field, therefore can easily obtain biological uptake thing as the purpose particle diameter.

As stated, state is imported into processing with between the face because each fluid is to keep independently, therefore can in the film fluid that forms, each fluid be mixed, and therefore can omit previously necessary ready-mixed operation.Thus, can be to obtain the biological uptake thing than in the past more low-yieldly.

What explain is that the appellation of the 1st, the 2nd in each fluid described herein representes that the fluidic n of a plurality of existence is individual, is the mark in order to discern, and also can have the fluid more than the 3rd.If use the fluid more than the 3rd, when the ribosomal manufacturing that contains composite emulsion particle or oil phase and water-phase component, be useful.

In the manufacturing of biological uptake thing, except that necessary pharmacological active substance, can in disperse phase or external phase, add various materials.For example; Carbohydrate with low molecule or high molecular modification material, for example amino acid, peptide, Transferrins,iron complexes, semi-lactosi or seminose etc.; Import the above-mentioned film fluid from independent paths; Mix with above-mentioned each fluid, thus can be through desirable modification material with the surface stabilization of biological uptake thing.In addition,, also be not limited to above-mentioned combination, can add in arbitrary fluid of disperse phase and external phase, according to circumstances also can add in two sides' the fluid down for pharmacological active substance.

The particle diameter of the biological uptake thing that obtains through above-mentioned operation, unnecessary because the ready-mixed of external phase and disperse phase becomes, uneven stuff and other stuff can not take place; In addition; Because can cast energy equably, compare with previous method, can carry out single dispersion.In addition, handle the gap of handling with portion, may command particle diameter through free adjustment the 1st with portion and the 2nd.

In addition; When the manufacturing of biological uptake thing; For example use drawdown pump Q shown in Figure 18 (A) suchly; With the 1st handle with portion 10 and the 2nd handle with the outside of portion 20, promptly be processed stream that liquid passes through become decompression state (comprising vacuum state) on every side, can deposit the gas of oxygen etc., lower boiling organic solvent, steam etc. and outgas or carry out desolventizing the air contained in the liquid or molten of being processed in emulsionization and the rrna chemical industry preface.Like this, the fluid that contains the biological uptake thing that obtains because between handling with face, mix is discharged with atomize with face from handling, so this fluidic surface-area increase, has the very high advantage of degassing desolventizing efficient.Like this degassing or desolventizing the permanent stability of handled thing (biological uptake thing) excellent.

In ribosomal method of manufacture as the biological uptake thing, make the arbitrary at least side who is processed liquid of disperse phase or external phase, contain as natural and synthetic phospholipid matter, their hydrogenated derivatives and in their mixture more than one.

Above-mentioned phosphatide; Particularly; Can enumerate and be selected from phosphatidylcholine, phosphatidylethanolamine, the glyceryl phosphatide class of phosphatidylserine, phosphatidic acid, POPG, PI, Val, Ovum Gallus domesticus Flavus lecithin, soybean lecithin, hydrogenated yolk lecithin, hydrogenated soy phosphatidyl choline etc.; Be selected from the sphingophospholipid class of ス Off イ Application go エ ミ リ Application, ceramide phosphoryl thanomin (ceramidephosphorylethanolamine), ceramide phosphoryl glycerine etc.; The PLPE class, digalactosyl diglyceride, the glycerine lipid of galactosyl diglyceride sulfuric ester etc. etc.

Except that above-mentioned, also can contain: amphiphilic cpds, ionic and nonionic surfactant, sphingoglycolipid (for example, galactosyl ceramide; Glycosyl ceramide, galactosyl ceramide sulfuric ester, lactosyl ceramides porcine, Sphingolipids,sialo G7; Sphingolipids,sialo G6, Sphingolipids,sialo G4), physiological bile salt (for example, Sodium cholic acid; Sodium Dehydrocholate, Sodium desoxycholate, Sodium glycocholate and Taurocholic acid sodium salt), saturated and unsaturated fatty acids or Fatty Alcohol(C12-C14 and C12-C18); The ester of ethoxylated fatty acid or Fatty Alcohol(C12-C14 and C12-C18) and these materials and ether, alkylaryl-Aethoxy Sklerol (for example tyloxapol), the ester of sugar or sugar alcohol and lipid acid or Fatty Alcohol(C12-C14 and C12-C18) and ether; Acetylize or ethoxylation list-and two glyceryl ester, synthesising biological decomposability polymkeric substance (the for example segmented copolymer of polyethylene oxide and polypropyleneoxide oxide compound), ethoxylation dehydrated sorbitol ester or sorbitan ether, amino acid; Polypeptide and protein (for example gelatin and BSA), sterols (for example plant sterol, SUV, Viteolin).

In the moity of biological uptake thing, have under the situation of unsaturated fatty acids,, preferably between handling, import nitrogen or the such rare gas element of argon gas, in this environment, handle with face in order to prevent the oxidation of lipid.For example, handle with portion and the 2nd the 1st and handle with the outside of portion, promptly be processed the stream that liquid passes through and be full of with above-mentioned rare gas element on every side.

In the manufacturing of biological uptake thing; The water-phase component that uses in water system dispersion solvent that uses in the external phase or the disperse phase; As long as be acceptable liquid on the pharmacology; Do not do special qualification, can enumerate water, damping fluid, ethanol, Ucar 35, DMSO 99.8MIN. (DMSO) or MIBK (MIBK) or their mixture etc.Wherein, preferably water or damping fluid.

In the manufacturing of biological uptake thing, the oil-phase component that uses in oil system dispersion solvent that uses in the external phase or the disperse phase except that the natural oil of VT 18, olive wet goods, can use synthetic oil.

In the manufacturing of biological uptake thing; In the disperse phase composition, contain under the situation of material with phase transition temperature; Will to adjust to phase transition temperature be+5～+ 45 ℃ TR handling the film fluid that form between the use face; After this, the biological uptake thing that will in the film fluid, obtain is chilled to below the phase transition temperature, obtains desirable biological uptake thing thus.The reason of carrying out quick-frozen is in order to be not cause the biological uptake thing aggegation that manufactures or unification, livering.

For example, the phase transition temperature of phosphatide body, dimyristoyl phosphatidyl choline are 23～24 ℃, and two palmityl phosphatidyl cholines are 41.0～41.5 ℃, and the distearyl phosphatidyl choline is 54.1～58.0 ℃, and hydrogenated soy phosphatidyl choline is about 53 ℃.

What explain is, rrna that obtains and microemulsion particle, and available preferred 0.45 μ m, more preferably the strainer of 0.22 μ m carries out sterile filtration.

In addition, through rrna and the microemulsion particle that the present invention obtains, more than one month, do not find the formation of visible agglomeration at dark cold place (4 ℃).Thereby, the rrna that obtains through the present invention and the excellent in stability of microemulsion particle.What explain is that the volume average particle size in the size-grade distribution of the biological uptake thing that obtains is 10～400nm, particularly excellent in stability.

Through the biological uptake thing that the present invention obtains, needing only in biology, to absorb is purpose, it is not done special the qualification; For example can be the medicament capsule, preparation absorbed through skin, oral prepns; Immunoadjuvant, artificial red blood corpuscle, the pharmaceuticals that kind of artificial thrombocyte etc. shows the material of certain effect in vivo; Material is used in the transmission that reaches the pharmaceutical cpd of drug delivery system, and gene imports carrier, or as makeup, is coated on paste formulation or lotion and the hair restoring and curing agent on the skin; Or food or food additives, protective foods, spices etc.

Like this; The method of manufacture of biological uptake thing of the present invention; Do not need indispensable till now preparation dispersion step, and, various medicines unequal coordinations or the unequal thermal history in the preparation dispersion state, the influence of the unequal energy amount of casting got rid of; Often produce new mixing field, therefore can obtain uniform particle diameter.And, handle the gap of handling with portion owing to can freely regulate the 1st easily with portion and the 2nd, therefore can freely control particle diameter.Thus, can simplify flow chart, compare with former method, can obtain desirable particle at short notice, Energy efficiency is good, and productivity is good.

Below, describe in more detail for disclosed embodiment of the present invention.But the present invention has more than and is defined in these embodiment.Embodiment J1～J4 and J9～J21 are relevant ribosomal embodiment, and embodiment J5～J8 is the embodiment of relevant microemulsion particle.

What explain is; In following embodiment; So-called " from central authorities "; Refer to such an extent that be the meaning of " from the 1st d1 of importing portion " of treatment unit shown in above-mentioned, Fig. 1 (A), the 1st fluid is meant that the above-mentioned the 1st is processed liquid, that the 2nd fluid is meant is above-mentioned, treatment unit shown in Fig. 1 (A) " that import from the 2nd d2 of importing portion, above-mentioned the 2nd is processed liquid.

(embodiment J1)

From the mixed solution of central authorities with 20% aqueous trehalose solution 240g and 10% Osmitrol 60g; Be heated to 85 ℃ as the 1st fluid; Carry out liquor charging with supply pressure/back pressure=0.13MPa/0.12Mpa, rotating speed 5000rpm; To mix, heating for dissolving hydrogenation (hydrogenation) soybean lecithin 12g, SUV 6g, 1; The solution of 3-butyleneglycol 24g, p-Hydroxybenzoate 1.2g imports the 1st processing and handles with between the face 2 with face 1 and the 2nd as the 2nd fluidic, and liquid effluent mixes with the mode of 90ml/min.Treatment time is that every 300g treatment capacity is 3.3min.In addition, liquid effluent is handled with after discharging between portion from each, is chilled to below 35 ℃.

Solution after the above-mentioned processing uses to have used with dynamic light scattering method and measures as the particle size distribution device (day machine dress (strain) goods, trade(brand)name microtrac UPA150) of measuring principle, and median size (volume) is 45.8nm as a result.

(embodiment J2)

From central authorities the mixed solution of 20% aqueous trehalose solution 240g and 10% Osmitrol 6g is heated to 85 ℃ as the 1st fluid; Carry out liquor charging with supply pressure/back pressure=0.11MPa/0.12Mpa, rotating speed 8000rpm; To mix, heating for dissolving hydrogenated soy phosphatidyl choline 12g, SUV 6g, 1; The solution of 3-butyleneglycol 24g, p-Hydroxybenzoate 1.2g imports the 1st processing and handles with between the face 2 with face 1 and the 2nd as the 2nd fluid, and liquid effluent mixes with the mode of 90ml/min.Treatment time is that every 300g treatment capacity is 3.3min.In addition, liquid effluent is handled with after discharging between portion from each, is chilled to below 35 ℃.

Solution after the above-mentioned processing uses to have used with dynamic light scattering method and measures as the particle size distribution device (day machine dress (strain) goods, trade(brand)name microtrac UPA150) of measuring principle, and volume average particle size is 21.6nm as a result.

(embodiment J3)

From central authorities the mixed solution of 20% aqueous trehalose solution 240g and 10% Osmitrol 60g is heated to 85 ℃ as the 1st fluid; Carry out liquor charging with supply pressure/back pressure=0.14MPa/0.12Mpa, rotating speed 3000rpm; To mix, heating for dissolving hydrogenated soy phosphatidyl choline 12g, SUV 6g, 1; The solution of 3-butyleneglycol 24g, p-Hydroxybenzoate 1.2g imports the 1st processing and handles with between the face 2 with face 1 and the 2nd as the 2nd fluid, and liquid effluent mixes with the mode of 90ml/min.Treatment time is that every 300g treatment capacity is 3.3min.In addition, liquid effluent is handled with after discharging between portion from each, is chilled to below 35 ℃.

Solution after the above-mentioned processing uses to have used with dynamic light scattering method and measures as the particle size distribution device (day machine dress (strain) goods, trade(brand)name microtrac UPA150) of measuring principle, and volume average particle size is 60.9nm as a result.

(embodiment J4)

From central authorities with the mixed solution of 20% aqueous trehalose solution 240g and 10% Osmitrol 60g as the 1st fluid, be heated to 85 ℃, with supply with pressure/back pressure=0.14MPa/0.25Mpa, rotating speed 5000rpm carries out liquor charging; To mix, heating for dissolving hydrogenated soy phosphatidyl choline 12g, SUV 6g, 1; The solution of 3-butyleneglycol 24g, p-Hydroxybenzoate 1.2g is as the 2nd fluid; Import the 1st processing and handle with between the face 2 with face 1 and the 2nd, liquid effluent mixes with the mode of 30ml/min.In addition, liquid effluent is handled with after discharging between portion from each, is chilled to below 35 ℃.

Solution after the above-mentioned processing uses to have used with dynamic light scattering method and measures as the particle size distribution device (day machine dress (strain) goods, trade(brand)name microtrac UPA150) of measuring principle, and volume average particle size is 36.8nm as a result.

(Comparative Example J 1)

In heating for dissolving hydrogenated soy phosphatidyl choline 10.5g, SUV 5.25g, 1; Add 20% aqueous trehalose solution 210g, 10% Osmitrol 52.5g in the liquid of 3-butyleneglycol 21g, p-Hydroxybenzoate 1.05g; Temperature adjustment to 85 ℃; (M technology society system ClearMixW-motion) is handled 10min with rotor 18000rpm/ ス Network リ one Application 17000rpm, is chilled to below 35 ℃ with each 6000rpm of rotor 6000rpm/ ス Network リ one Application thereafter to use homogenizer.

Solution after the above-mentioned processing uses to have used with dynamic light scattering method and measures as the particle size distribution device (day machine dress (strain) goods, trade(brand)name microtrac UPA150) of measuring principle, and volume average particle size is 63.8nm as a result.

(Comparative Example J 2)

In heating for dissolving hydrogenated soy phosphatidyl choline 10.5g, SUV 5.25g, 1; Add 20% aqueous trehalose solution 210g, 10% Osmitrol 52.5g in the solution of 3-butyleneglycol 21g, p-Hydroxybenzoate 1.05g; Temperature adjustment to 85 ℃, use homogenizer (ClearMix) to loose with the 8000rpm rough segmentation after, use emulsification dispersion machine (M technology society system; SS5) handle for 85 ℃ with rotating speed 5000rpm, temperature, liquid effluent is 30ml/min.

Solution after the above-mentioned processing uses to have used with dynamic light scattering method and measures as the particle size distribution device (day machine dress (strain) goods, trade(brand)name microtrac UPA150) of measuring principle, and volume average particle size is 56.8nm as a result.

[table 17]

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Comparative example 1	Comparative example 2
							Rotating speed [rpm]	5000	8000	3000	5000	18000/17000	5000
Treatment time [min]	3.3	3.3	3.3	10	10	10
							Particle diameter D 50[nm]	45.8	21.6	60.9	36.8	63.8	56.8
Energy is cast rate [-]	0.074	0.351	0.019	0.257	1	0.93

Attention: treatment capacity all is set at 300g, forms ultimate density and is set at necessarily.

The treatment time of embodiment 1～4 is set at 300g and handles the needed time

It is shown in table 17 that (what explain is; Embodiment 1～4 in the table and comparative example 1～2; Represent the foregoing description J1～J4 and Comparative Example J 1～J2) respectively, energy needed in rrnaization is compared with Comparative Example J 1; Embodiments of the invention J1 is that about 1/14th, embodiment J2 is that about 1/3rd, embodiment J3 is about 1/53rd, and embodiment J4 is about 1/4th.In addition, compare with Comparative Example J 2, embodiments of the invention J1 is about 1/13rd, and embodiment J2 is that about 1/3rd, embodiment J3 is about 1/49th, and embodiment J4 is about 1/4th.Hence one can see that, and the Energy efficiency of the method for manufacture of the foregoing description is excellent.

(embodiment J5)

The solution that will among water for injection 853.5g, mix concentrated glycerin 22.1g and pH adjustment agent (aqueous sodium hydroxide solution) from central authorities is as the 1st fluid; Carry out liquor charging with supply pressure/back pressure=0.020MPa/0.01Mpa, rotating speed 1000rpm; With interpolation PGE1 5mg in the mixed solution of refining sweet oil 100g and highly purified Ovum Gallus domesticus Flavus lecithin 18g, oleic acid 2.4g and then carry out solution that stirring and dissolving forms as the 2nd fluid; Import the 1st processing and handle with between the face 2 with face 1 and the 2nd, liquid effluent mixes with the mode of 50ml/min.Treatment time is that every 300g treatment capacity is 6min.

Solution after the above-mentioned processing uses to have used with the laser diffraction and scattering method and measures as the particle size distribution device (SIMAZU society system, trade(brand)name SALD-7000) of measuring principle, and volume average particle size is 70.4nm as a result.

(embodiment J6)

The solution that will among water for injection 853.5g, mix concentrated glycerin 22.1g and pH adjustment agent (aqueous sodium hydroxide solution) from central authorities is as the 1st fluid; Carry out liquor charging with supply pressure/back pressure=0.010MPa/0.01Mpa, rotating speed 2000rpm; With interpolation PGE1 5mg in the mixed solution of refining sweet oil 100g and highly purified Ovum Gallus domesticus Flavus lecithin 18g, oleic acid 2.4g and then carry out solution that stirring and dissolving forms as the 2nd fluid; Import the 1st processing and handle with between the face 2 with face 1 and the 2nd, liquid effluent mixes with the mode of 50ml/min.Treatment time is that every 300g treatment capacity is 6min.

Solution after the above-mentioned processing uses to have used with the laser diffraction and scattering method and measures as the particle size distribution device (SIMAZU society system, trade(brand)name SALD-7000) of measuring principle, and volume average particle size is 38.3nm as a result.

(embodiment J7)

The solution that will among water for injection 853.5g, mix concentrated glycerin 22.1g and pH adjustment agent (aqueous sodium hydroxide solution) from central authorities is as the 1st fluid; Carry out liquor charging with supply pressure/back pressure=0.015MPa/0.01Mpa, rotating speed 1500rpm; The solution that interpolation PGE1 5mg and then stirring and dissolving in the mixed solution of refining sweet oil 100g and highly purified Ovum Gallus domesticus Flavus lecithin 18g, oleic acid 2.4g are formed is as the 2nd fluid; Import the 1st processing and handle with between the face 2 with face 1 and the 2nd, liquid effluent mixes with the mode of 50ml/min.Treatment time is that every 300g treatment capacity is 6min.

Solution after the above-mentioned processing uses to have used with the laser diffraction and scattering method and measures as the particle size distribution device (SIMAZU society system, trade(brand)name SALD-7000) of measuring principle, and volume average particle size is 68.5nm as a result.

(embodiment J8)

The solution that will among water for injection 853.5g, mix concentrated glycerin 22.1g and pH adjustment agent (aqueous sodium hydroxide solution) from central authorities is as the 1st fluid; Carry out liquor charging with supply pressure/back pressure=0.040MPa/0.01Mpa, rotating speed 1500rpm; The solution that interpolation PGE1 5mg and then stirring and dissolving in the mixed solution of refining sweet oil 100g and highly purified Ovum Gallus domesticus Flavus lecithin 18g, oleic acid 2.4g are formed is as the 2nd fluid; Import the 1st processing and handle with between the face 2 with face 1 and the 2nd, liquid effluent mixes with the mode of 100ml/min.Treatment time is that every 300g treatment capacity is 3min.

Solution after the above-mentioned processing uses to have used with the laser diffraction and scattering method and measures as the particle size distribution device (SIMAZU society system, trade(brand)name SALD-7000) of measuring principle, and volume average particle size is 70.1nm as a result.

(Comparative Example J 3)

In water for injection 257.08g, adding concentrated glycerin 6.65g mixes.In addition, stirring and dissolving is made with extra care sweet oil 30.12g, highly purified Ovum Gallus domesticus Flavus lecithin 5.42g, oleic acid 0.73g, to wherein adding PGE1 1.5mg, and then stirring and dissolving.It is added in the mixed liquid of the water for injection before adjusted and glycerine; Use homogenizer (M technology society system; ClearMixW-motion) handle 10min with rotor 18000rpm/ ス Network リ one Application 17000rpm, about 5 with sodium hydroxide adjustment pH, obtain the lipomul of PGE1.

Solution after the above-mentioned processing uses to have used with the laser diffraction and scattering method and measures as the particle size distribution device (SIMAZU society system, trade(brand)name SALD-7000) of measuring principle, and volume average particle size is 117.3nm as a result.

(Comparative Example J 4)

In water for injection 257.08g, adding concentrated glycerin 6.65g mixes.In addition, stirring and dissolving is made with extra care sweet oil 30.12g, highly purified Ovum Gallus domesticus Flavus lecithin 5.42g, oleic acid 0.73g, to wherein adding PGE1 1.5mg, and then stirring and dissolving.It is added in the mixed liquid of the water for injection before adjusted and glycerine, and (M technology society system, SS5), with rotating speed 5000rpm processing 6min, liquid effluent is 50ml/min to use the emulsification dispersion machine.Thereafter about 5 with sodium hydroxide adjustment pH, obtain the lipomul of PGE1.

Solution after the above-mentioned processing uses to have used with the laser diffraction and scattering method and measures as the particle size distribution device (SIMAZU society system, trade(brand)name SALD-7000) of measuring principle, and volume average particle size is 109.5nm as a result.

[table 18]

	Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Comparative example 3	Comparative example 4
							Rotating speed [rpm]	1000	2000	1500	1500	18000/17000	5000
Treatment time [min]	6	6	6	3	10	6
							Particle diameter D 50[nm]	70.4	38.3	68.5	70.1	117.3	109.5
Energy is cast rate [-]	0.05	0.40	0.17	0.08	1	0.56

Attention: treatment capacity all is set at 300g, forms ultimate density and is set at necessarily.

The treatment time of embodiment 5～8 is set at 300g and handles the needed time

It is shown in table 18 that (what explain is; Embodiment 5～8 in the table and comparative example 3～4, represent the foregoing description J5～J8 and Comparative Example J 3～J4) respectively, in micro emulsion liquefaction energy needed, compare with Comparative Example J 3; Embodiments of the invention J5 is about 1/20th; Embodiment J6 is about 1/3rd, and embodiment J7 is about 1/6th, and embodiment J8 is about 1/13rd.In addition, compare with Comparative Example J 4, embodiments of the invention J5 is about 1/11.2nd, and embodiment J6 is about 1/1.4th, and embodiment J7 is about 1/3.3rd, and embodiment J8 is about 1/7.0th.Hence one can see that, and the Energy efficiency of the method for manufacture of the foregoing description is excellent.

(embodiment J9～J21)

Secondly, checking is because the difference of the particle diameter of the caused biological uptake thing of difference of the cooling temperature after dropping into temperature and handling.

The liquid that will in the 10g VT 18, disperse the 1.2g hydrogenated soy phosphatidyl choline is as oil phase; The liquid that will in the 863g Purified Water, dissolve 25g glycerine is as water; Condition with table 19 handles that (what explain is that the embodiment 9～21 in the table represents the foregoing description J 9～J21).Utilize as Fig. 1 (A) shown in, can be near the treatment unit that mixes uniformly in the film fluid of processing that set, that at least one side is rotated with respect to the opposing party with face 1, formation between 2 to subtend each other discretely; Make oil phase in the film fluid with water interflow, on one side uniform mixing carry out emulsification on one side and disperse.

[table 19]

* the phase transition temperature of hydrogenated soy phosphatidyl choline is about 53 ℃.

The mensuration result of particle diameter is recorded in table 20, and (what explain is, the embodiment 9～21 in the table represents the foregoing description J9～J21)

[table 20]

	Particle diameter D 50[nm]
		Embodiment 9	568.7
Embodiment 10	263.5
		Embodiment 11	84.6
Embodiment 12	72.9
		Embodiment 13	78.5
Embodiment 14	69.4
		Embodiment 15	326.8
Embodiment 16	70.8
		Embodiment 17	139.6
Embodiment 18	385.7
		Embodiment 19	368.9
Embodiment 20	376.9
		Embodiment 21	584.3

(K) resin particle

Below, the generation of the resin particle among the present invention is described.

The generation of this resin particle, as Fig. 1 (A) shown device, can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, between 2, on one side one side uniform mixing carries out by the strong hand.

At first; From the 1st d1 of importing portion as 1 stream; The fluid that will contain at least a aqueous vehicles as the 1st fluidic; Importing can near discretely each other subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, between 2, the film fluid that generation is made up of the 1st fluid between this processing is with face.

Then, from the 2nd d2 of importing portion, will in the solvent that with respect to resin is solvability and consistency, dissolve as other stream, preferred molecular dispersion the fluid of at least a kind of resin as the direct above-mentioned film fluid that constitutes by the 1st fluid of the 2nd fluid.

As stated, between the processing of supply with pressing and being rotated through fluidic is with the face pressure equilibrium of applied pressure and will can form the film fluid apart from the processing of having controlled with face 1, between 2.And, form the film fluid at the interflow of the 1st fluid and the 2nd fluid in this film fluid.The 1st fluid and the 2nd fluid interflow in this film fluid and mixed is through separating out or emulsification generates resin particle.What explain is, in the 1st fluid or the 2nd fluid, adds tensio-active agent usually, obtains having disperseed at aqueous phase the aqueous resin microparticle dispersion of resin particle.In addition, under situation of the present invention, can be with resin covert, also must be with resin covert.

In addition, in above-mentioned " emulsification ", comprise through make the operation of resin emulsion particle at the above-mentioned processing resin that dissolving (molecular dispersion) in the 1st fluid and the 2nd fluid interflow, emulsification film fluid in the film fluid between face.Resin emulsion particle making is under the situation of resin particle itself; Or carry out desolventizing through the fluid that will contain the resin emulsion particle and take out under the situation of resin emulsion particle; Through this resin emulsion particle, also can obtain the water dispersion and the resin particle of resin particle.

What explain is, owing to can carry out above-mentioned reaction with face 1, between 2 and get final product handling, therefore, also can import the 2nd fluid from the 1st d1 of importing portion on the contrary with above-mentioned, imports the 1st fluid from the 2nd d2 of importing portion.That is, the appellation of each fluidic the so-called the 1st, the 2nd is that the fluidic n of a plurality of existence of expression is individual, and just also can there be the fluid more than the 3rd in the mark in order to discern.

The particle diameter of the resin particle that obtains, single dispersity, or the control of crystal type can be through change handling with the rotating speed of face 1,2 or processing with face 1, distance and film flow rate of fluid or temperature between 2, and perhaps material concentration etc. is regulated.Like this, can obtain comparing the little monodispersed resin particle of volume average particle size with the resin particle that reaction method through till now obtains.In addition, efficient obtains resin particle well serially, and it is also good to make efficient, can tackle mass production.In addition, treatment unit of the present invention can use general amplification notion according to the turnout of necessity, can carry out the maximization of body.In addition, can obtain resin particle equably in low-yield ground.

As the solvent that makes resin, molecular dispersion, as long as resin is shown solvability or consistency, do not do special qualification, as concrete solvent, can separately or make up more than 2 kinds and use toluene, ETHYLE ACETATE, butylacetate, methyl ethyl ketone, MIBK etc.

As the aqueous vehicles of using among the present invention, can be independent water, also can and water and blendable solvent.As blendable solvent, can be alcohol (methyl alcohol, Virahol, terepthaloyl moietie etc.) etc.

In addition, also can use the fluid that contains at least a kind of molten resin, replace above-mentioned make resin dissolves or molecular dispersion in to the solvent of resin as solvability and consistency fluid.That is, in the film fluid, molten resin emulsification is disperseed, after this resin solidization is implemented.Described here resin fusion must be to heat to the situation of the temperature more than the fusing point, demonstrate as liquid fluidic character for the situation middle finger of crystalline resin for example.In addition, under the situation of amorphous resin, refer to such an extent that be that the heat viscosity of resin, resin begins to descend, resin demonstrates as the fluidic behavior, reaches the temperature more than the glass transformation temperature as benchmark.At this moment, the fusion of resin can only be carried out in resin, also can be in the solvent that does not have solvability and consistency for resin, to carry out.In addition, the meaning opposite with fusion represented in the solidification of resin.Thus; For molten resin; Owing to just heated and made its fusion, after the emulsification dispersion treatment, can cool off, therefore can handle, can reduce in fact thermal history (summation of=(temperature * time)) in the short period of time for resin, therefore can reduce the risk of the hydrolysis of resin.And then therefore compared and to improve emulsification dispersion treatment temperature with former method of manufacture.Therefore, resin viscosity is reduced more carry out the emulsification dispersion treatment, the result can be with the low-yield size-grade distribution that obtains as purpose.In addition, though at high temperature molten resin is separated out or emulsification dispersive situation under because its recoverable amount is little, can be with equipment miniaturization, processing ease, security is also high.

And, according to the method for manufacture of aqueous resin microparticle dispersion of the present invention, can omit in the technology till now for successively with the particle sectionalization of resin and the ready-mixed operation of indispensable, resin and aqueous vehicles.Promptly; In the present invention; Before above-mentioned processing imports with face 1, between 2, need not be pre-mixed resin and aqueous vehicles at above-mentioned fluid so that resin is dispersed in the ready-mixed operation of the state in the aqueous vehicles with the state of oversize particle, can be with the direct gatherer of each fluid.Therefore, not only simplified operation, had simultaneously and can avoid because the thermal history of the reduction of the complicated yield that causes of operation, the resin that takes place in the time of can omitting ready-mixed, the advantage of the hydrolysis risk etc. of resin of can reducing.What explain is, before above-mentioned processing was with face 1, importing between 2, with the 1st fluid, the part of the 2nd fluidic constituent parts hybrid resin and aqueous vehicles was not equivalent to above-mentioned " ready-mixed " at above-mentioned fluid.This is because be to make resin have as the processing of fluidic movement, not be equivalent to as former for the particle processing of sectionalization successively with resin.

But the method for manufacture that the application's invention relates to not is to get rid of the ready-mixed operation fully.Thereby, also can according to circumstances be provided with and former identical ready-mixed operation.

In addition, through the cooling or the above-mentioned processing of heating with between face, can obtain desirable resin particle.Particularly, handle with face 1 and the 2nd processing to be provided with under the situation of temperature head on face 2 the 1st, can in the film fluid, convection current take place, therefore, have thus further to make and manage throughout with face 1, the promoted advantage of pressure uniform mixing between 2.

In addition, also can be according to its purpose to handling with irradiation ultraviolet radiation between face (UV).

And; Through with above-mentioned separate out or the emulsification dispersion treatment can guarantee to reduce pressure or the container of vacuum state in carry out, make and handle 2 sides that back fluid (aqueous resin microparticle dispersion) is discharged from and become decompression or vacuum state, the degassing or the above-mentioned fluidic desolventizing of the gas that carries out being contained in gas that each fluidic interflow in the above-mentioned film fluid taken place and the above-mentioned fluid.Thus, though with separate out dispersion treatment and substantially carry out simultaneously handling with the fluid that contains resin particle between face and discharging with atomize with face under the situation that desolventizing handles from handling, so this flow surface amasss increase, desolventizing efficient is very high.Therefore than till now also simply, 1 operation is separated out or emulsification dispersion treatment and desolventizing processing in fact.

In addition,, for example, can cool off, carry out the solidification of molten resin and handle fluid (aqueous resin microparticle dispersion) after the processing of just having discharged through separating out or the emulsification dispersion treatment can carried out in the thermoregulated container with above-mentioned.Thus can be with being cooled to the stable temperature province of resin particle, promptly rapidly through the resin particle of separating out or emulsification disperses to obtain, below the above-mentioned fusing point, or below the second-order transition temperature.In addition, through with heating in the container, also can improve the efficient that above-mentioned desolventizing is handled and the degassing is handled.

As above-mentioned resin, any resin all can use, particularly, but illustration vinyl polymerization based thermoplastic resin (styrene resin; Olefine kind resin, acrylics, Halogen resin, vinyl ester resinoid or derivatives thereof etc.); Condensation based thermoplastic resin (polyester resin, polyamide-based resin, polyurethanes resin; Gather (sulphur) ether resin, polycarbonate resinoid, polysulfones resin; Polyimide based resin etc.), from the resin (cellulose ester resinoid etc.) of natural goods, redix etc.These resins can use separately, also can make up use more than two kinds.No matter above-mentioned in addition resin is crystallinity or amorphousness, all can implement.

As styrene resin; Styrene monomer (the vinylbenzene of can giving an example; Alpha-methyl styrene, Vinyl toluene etc.) homopolymer or multipolymer (PS, styrene-ethylene base toluene multipolymer; Styrene-multipolymer etc.); Styrene monomer is the multipolymer of polymerizable monomer (styrene-acrylonitrile copolymer (AS resin), (methyl) acrylic styrene copolymer (MS resin etc.), vinylbenzene-Maleic Acid, Anhydrous anhydride copolymer together; The segmented copolymer of styrene-butadiene block copolymer etc.; At the graftomer (impact resistant polystyrene (HIPS, or grafting rubbers polystyrene resins)) that the existence of rubber constituent forms down to the graft copolymerization of major general's styrene monomer, acrylonitrile-butadiene-styrene copolymer (ABS resin); Replace the divinyl rubber B of above-mentioned ABS resin and used graft copolymer (the AES resin of the rubber constituent of ethylene propylene rubber E, acrylic rubber A, chlorinatedpolyethylene C, vinyl acetate polymer etc.; AAS resin, the AXS resin of ACS resin etc.), replacing the vinyl cyanide of above-mentioned ABS resin and having used (methyl) acrylic acid or the like is graft copolymer (methyl methacrylate butadiene rubber-styrene copolymerized compound (MBS resin) etc.) of monomer (TEB 3K etc.) etc.

As olefine kind resin, can be the homopolymer or the multipolymer of α-C2-6 alkene, for example can enumerate Vilaterm; Vestolen PP 7052; Ethylene-propylene copolymer gathers the homopolymer or the multipolymer of the alkene of (methylpentene-1) etc., the monomeric multipolymer of alkene and multipolymer (vinyl-vinyl acetate copolymer; Ethene-(methyl) PEMULEN TR2, ethene-(methyl) Yodo Sol GH 28 etc.).

As acrylics, (methyl) acrylic monomer of can giving an example ((methyl) vinylformic acid, (methyl) vinylformic acid C1-18 alkyl ester; (methyl) vinylformic acid hydroxyalkyl acrylate; (methyl) glycidyl acrylate, (methyl) vinyl cyanide etc.) homopolymer or multipolymer, that for example gathers (methyl) methyl acrylate etc. gathers (methyl) propenoate; TEB 3K-(methyl) PEMULEN TR2; TEB 3K-propenoate-(methyl) PEMULEN TR2, TEB 3K-(methyl) Yodo Sol GH 28, (methyl) acrylic styrene copolymer (MS resin etc.) etc.

As the Halogen resin, for example can enumerate polyvinyl chloride resin, vinylchlorid-VINYL ACETATE MONOMER (VAM) multipolymer, vinylidene chloride resin, fluoro-resin etc.As vinyl ester resinoid or its water-insoluble verivate; For example can enumerate the monomer or the multipolymer (Yodo Sol VC 400, vinyl-vinyl acetate copolymer etc.) of vinyl esters of carboxylic acids, the saponified (Z 150PH of saponification deg below 50% of these materials; The vinyl alcohol resinoid of ethylene-vinyl alcohol copolymer etc.); From the verivate (for example, PVF, the polyvinyl acetal-based resin of polyvinyl butyral acetal etc. etc.) of saponified (vinyl alcohol resinoid) etc.

As polyester resin, can enumerate and use dicarboxylicacid composition, diol component, hydroxycarboxylic acid (acid of オ キ シ カ Le ボ Application); The various resins of lactone, for example, polyethyleneterephthalate; Gather (trimethylene terephthalate), polytrimethylene terephthalate, polybutylenes butylene terephthalate; Gather (1,4-cyclohexyl dimethylene terephthalate, Polyclear N 100; That gathers naphthalic acid fourth diester etc. gathers C2-6 alkylidene group-square acid number resinoid, as the copolyesters of staple (for example, more than the 50w%) (for example contains C2-6 alkylidene group-aryl esters unit; Copolymer composition is to have the polyoxy C2-4 aklylene glycol of oxygen alkylidene unit and the aliphatic dicarboxylic acid of C6-12, m-phthalic acid, the copolyesters of the asymmetry aromatic dicarboxylic acid of phthalandione etc. etc.); Gather the aryl esters resinoid, the aromatic polyester-based resin of liquid crystalline polyester etc.; Gather C2-6 alkylidene group-barkite, gather C2-6 alkylidene group-succinate, gather (the C2-6 aklylene glycol-C2-10 aliphatic dicarboxylic acid ester) of C2-6 alkylidene group-adipic acid ester etc.; Polyhydroxycarboxyliacid acid resinoid (for example, Sodium bromoacetate homopolymer, SRU or POLYACTIC ACID, oxyacetic acid-lactic acid copolymer etc.); The polylactone resinoid (for example; Polycaprolactone etc. gather C3-12 lactone resin etc.), copolyesters of these materials (for example, polycaprolactone-poly-succinic fourth diester copolymer resins etc.) etc.Polyester resin also can contain amino-formate bond.And polyester resin also can have biodegradability.

Polyamide-based resin for example, can be enumerated fatty polyamide resinoid (for example, polymeric amide 46, polyamide 6; Polyamide 66, polymeric amide 11, polymeric amide 12, polyamide 6 10, polyamide 6 12; Polyamide 1010, polymeric amide 1012, polymeric amide 1212 etc.), copolyamide is (for example; Polyamide 6/11, polyamide 6/12, polyamide 66/11, polyamide 66/12 etc.); The ester ring type polyamide-based resin; Aromatic polyamide resinoid etc.The dicarboxylicacid composition of polyamide-based resin also can contain the dimeracid unit.And polyamide-based resin also can have biodegradability.

As the polyurethanes resin; For example; But illustration diisocyanates (the aliphatic diisocyanate class of hexamethylene diisocyanate etc., 1, the alicyclic diisocyanate class of 4-cyclohexyl diisocyanate, isophorone diisocyanate etc.; Tolylene diisocyanate, ditan-4; 4 '-vulcabond, 1, aromatic diisocyanate class or its hydrogenation diisocyanates such as 5-naphthalene diisocyanate, the aromatic-aliphatic diisocyanates of xylylene vulcabond etc. or its hydrogenation diisocyanates etc.); Polyalcohols (for example, the polyether glycol of polyester polyol, polytetramethylene ether diol etc., polycarbonate polyol etc.); The polyurethanes resin that obtains through reaction as required with the chain extension agent.

As gathering (sulphur) ether resin, for example, comprise; Polyoxy alkylidene resinoid (stabilized polyether polyols or all or the copolymerization acetal-based resin, polyether polyols, the polyoxy C1-4 aklylene glycol of polyoxy tetramethylene glycol etc.); The ppe resinoid; The ppe ketone resin, polysulphide resinoid (the polysulfide ether resins of polyphenylene sulfide or its multipolymer etc.), polyetherketone resinoid (comprising the polyetheretherketone resinoid) etc.

As the polycarbonate resinoid, comprise the aromatic polycarbonate fat that the bisphenols with bisphenol A-type polycarbonate resin etc. is the basis, the aliphatic poly carbonic ether of Diethylene Glycol diene propyl carbonate etc. etc.

As the polysulfones resin, but the illustration polysulfone resin, polyethersulfone resin, polyaryl sulfone resin etc.As polyimide based resin, but illustration polyetherimide resinoid, polyamideimides resin, polybenzimidazole resinoid etc.

As derivatived cellulose, can enumerate cellulose esters (for example, the Vladipor UAM 500 of cellulose diacetate, cellulosic triacetate etc. (rhodia); Cellulose propionate; Cellulose butylate, Vladipor UAM 500 propionic ester, the acyl group Mierocrystalline cellulose of cellulose acetate butyrate etc.; Cellulosic inorganic acid ester etc.), cellulosecarbamate class (Mierocrystalline cellulose phenylcarbamate etc.) etc.What explain is if necessary, as the water-insoluble cellulose ethers, for example, also can use TKK 021, sec.-propyl Mierocrystalline cellulose, the alkylcellulose of butyl cellulose etc.; The aralkyl Mierocrystalline cellulose of benzyl cellulose etc.; Cyano ethyl Mierocrystalline cellulose etc.

In thermoplastic resin, also comprise thermoplastic elastomer (for example, polyamide-based elastomerics; Polyester elastomer, polyurethanes elastomerics, polystyrene type elastomerics; The polyolefins elastomerics, polyvinyl chloride elastomerics, fluorine analog thermoplastic elastomer etc.); The thermoplastic silicone resin, natural resin or derivatives thereof etc.

As epoxy resin, can enumerate the ring-opening polymerization polymer of polyepoxide (19), polyepoxide (19) with contain active hydrogen based compound (D) { water; Polyvalent alcohol [above-mentioned divalent alcohol (11) and the polyvalent alcohol more than 3 yuan (12)]; Dicarboxylicacid (13), the poly carboxylic acid more than 3 yuan (14), polyamines (16); Polythiol (17) etc. } addition polymer, or the cured article of the acid anhydrides of polyepoxide (19) and dicarboxylicacid (13) or the poly carboxylic acid more than 3 yuan (14) etc.

In these resins, optimization styrene resinoid for example, olefine kind resin, acrylics; The Halogen resin, vinyl ester resinoid or derivatives thereof (polyvinyl acetal-based resin etc.), polyester resin, polyamide-based resin; The polyurethanes resin gathers (generation) ether resin, polycarbonate resinoid, polysulfones resin; Polyimide based resin, and cellulose ester resinoid (rhodia resinoid etc.), epoxy resin.In addition, also preferred Biodegradable resin, for example, aliphatic polyester-based resin (for example, polylactic acid resin or gather C3-12 lactone resin etc.), the Biodegradable polyester resinoid of polyesteramide etc., vinyl alcohol resinoid, above-mentioned derivatived cellulose.

In addition, above-mentioned resin also can be the mixing thing of the resin that contains tinting material and implements.

As tinting material, known dye well pigment all can use, and for example, can use carbon black, aniline black dyestuffs, iron oxide black, naphthol yellow S, Hansa Yellow (10G; 5G, G), cadmium yellow, Zh 1, loess, chrome yellow, titan yellow, polyazo is yellow, oil yellow; HansaYellow (GR, A, RN, R), Pigment Yellow 73 L, diarylide yellow (G, GR), permanent yellow (NCG), Vulcanfast Yellow (5G; R), tartrazine lake, quinoline yellow lake, the yellow BGL of anthracene, isoindolinone is yellow, Indian red, the red lead, plumbous red, cadmium red; Cadmium mercury is red, antimony red, and permanent bordeaux 4R, p-nitroaniline red, red as fire, the solid forever scarlet G of p-chloro-o-nitroaniline red, Lithol, solid very forever scarlet, good carmine BS; Permanent bordeaux (F2R, F4R, FRL, FRLL, F4RH), solid forever scarlet VD, Vulcan permanent Rubine B, brilliant scarlet G G, Lithol Rubine GX; Permanent bordeaux F5R, brilliant carmine 6B, pigment scarlet 3B, the 5B of Bordeaux, Tolylamine maroon, permanent Bordeaux F2K, helio Bordeaux BL, the 10B of Bordeaux, BON maroon Light; BON maroon medium, eosine lake, rhodamine color lake B, rhodamine color lake Y, alizarine lake, 3B thioindigo red B, thioindigoid maroons, oil red, quinacridone is red; Pyrazolone red, polyazo red (poly azo red), molybdenum red (chrome vermilion), benzidine orange, pyrene ketone orange, oil orange, cobalt blue, cerulean blue, alkali blue lake; Peacock blue lake, victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, durable sky blue, indanthrene blue (RS, BC), indigo (indigo); Ultramarine, dark blue, anthraquinone is blue or green, Gu VT B, pyoktanin blue rowland color lake, cobalt violet (cobalt), manganese violet (manganese), dioxane VT; The anthraquinone VT, chrome green, zinc green, chromic oxide, guignet's green, emerald green, pigment green B, the green B of naphthols; Green gold, sour green lake, 4 basic green 4 color lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc oxide, lithopone and their mixture.

And, also can in the fluid of at least a kind of above-mentioned fluidic, contain dispersion agent and implement.As dispersion agent, it is not done special the qualification, under the situation of aqueous vehicles; Can enumerate Z 150PH, polyoxyethylene glycol, polyethylene oxide; Vinylpyrrolidone polymer, water-soluble acrylic resin, water-soluble phenylethene resinoid; The water soluble resin of Vinylpyrrolidone polymer, ether of cellulose resinoid etc. or contain the water-soluble sugar compsn of oligosaccharides; Even under the situation of other solvent, also can use known tensio-active agent, can use the dispersion stabilizer that is selected from cationic surfactant, anionic surfactant, the nonionic surfactant etc.These tensio-active agents also can more than 2 kinds and be used.

As the concrete example of cationic surfactant, can enumerate dodecyl chlorination ammonium, dodecyl bromination ammonium, Trimethyllaurylammonium bromide, dodecyl chlorination pyridine, dodecyl bromination pyridine, cetyl trimethylammonium bromide etc.

As anionic surfactant's concrete example, can enumerate sulphonate (X 2073, arylalkyl polyethers sodium sulfonate, 3,3-two sulfone diphenyl ureas-4; 4-diazonium-bis-amino-8-naphthols-6-sodium sulfonate, ortho-carboxyl benzene-azo-xylidine, 2,2,5; 5-tetramethyl--triphenyl methane-4,4-diazonium-two-β-Nai Fen-6-sodium sulfonate etc.), sulfuric acid (sodium lauryl sulphate, Trombovar, pentadecyl sodium sulfate; Sodium octyl sulfate etc.), soap (sodium oleate, sodium laurate, Sodium decanoic acid; Sodium octoate, Sodium n-caproate, potassium stearate, calcium oleate etc.) etc.

As nonionic surfactant, the polyethylene oxide of can giving an example, polypropyleneoxide; The combination of polypropyleneoxide and polyethylene oxide; The ester of polyoxyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, the ester of higher fatty acid and polyoxyethylene glycol; The ester of higher fatty acid and polypropyleneoxide, sorbitan ester etc.

Imported in making under the situation of water dispersion of vibrin etc. of carboxyl,, also can in above-mentioned fluid, contain the part or all of polar group of the carboxyl etc. of dispersion surface in order in above-mentioned fluid, to utilize the neutral stabilization of dispersion-s.

As the alkaline matter that can in above-mentioned neutralization, use, for example, can enumerate the amine compound that ammonia or triethylamine are representative, or sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate etc. are the inorganic base of representative.

As above-mentioned amine compound; Particularly; Can enumerate headed by ammonia, monomethyl amine, dimethyl amine, Trimethylamine, single ethylamine, DIETHANOL AMINE, triethylamine, single n-propyl amine, dimethyl--n-propyl amine, monoethanolamine, diethylolamine or the trolamine, N-carbinolamine, N-amino ethyl ethanolamine, N methyldiethanol amine, monoisopropanolamine, HSDB 338, tri-isopropanolamine, N; N-dimethylethanolamine or N, N-dimethyl propanol amine etc.Particularly preferably be triethylamine, monoethanolamine, diethylolamine, trolamine, N, N-dimethylethanolamine, or N, N-dimethyl propanol amine etc.Also can these amine compound also be used more than 2 kinds in addition.

In addition, the resin that obtains is being used for electrophoto-graphic toner situation etc., in the fluid of the method for manufacture of above-mentioned resin particle; Also can use and contain above-mentioned tinting material or antistatic agent, releasing agent, external additive; Magnetic carrier, at least a kind fluid in the conducting powder is implemented.

As releasing agent, preferably use wax.As wax, can use known material, for example, can enumerate polyolefin-wax (polyethylene wax, Poly Propylene Wax etc.); Long chain hydrocarbon (paraffin, Sasolwax etc.); Gather alkanoic acid ester (POLISHING WAX-103, montanin wax, trimethylolpropane tris behenate, tetramethylolmethane four behenates, tetramethylolmethane diacetate esters two behenates, glycerol tri-docosanoic acid ester, 1,18-18 decane divalent alcohol SUNSOFT Q-182Ss etc.); Gather alkanol ester (trimellitic acid three stearyl esters, toxilic acid distearyl ester etc.); Gather alkanoic acid acid amides (quadrol two mountain Yu base acid amides etc.); Many alkylamides (trimellitic acid three stearylamides etc.); And dialkyl ketone (distearyl ketone etc.) etc. contain carbonyl wax etc.

As antistatic agent, known material all can use, and for example, is nigrosine class dyestuff; Triphenylmethane dye contains the chromium metal complex dyes, molybdic acid inner complex pigment, rhodamine class dyestuff; Alcoxyl base class amine, quaternary ammonium salt (comprising fluorine sex change quaternary ammonium salt), alkylamide, the monomer of phosphorus or compound; The monomer of tungsten or compound, fluorine are promoting agent, and salicylic acid metal salt reaches, the metal-salt of salicyclic acid derivatives etc.

Particularly, can enumerate the BONTRON 03 of nigrosine class dyestuff, the BONTRON P-51 of quaternary ammonium salt; The BONTRON S-34 of containing metal azoic dyestuff, the E-82 of hydroxynaphthoic acid metalloid complex compound, the E-84 of salicylic acid metal complex; The E-89 of phenolic condensate (above, east chemical industry society system), the TP-302 of quaternary ammonium salt molybdenum complex, TP-415 (the industrial society of above, hodogaya chemical system); The Copy Charge PSY VP2038 of quaternary ammonium salt, the Copy Blue PR of triphenyl methane verivate, the Copy Charge NEG VP2036 of quaternary ammonium salt; Copy Charge NX VP434 (above, He Xisite society system), LRA-901 is as the LR-147 of boron complex (Japanese Carlit society system); Copper phthalocyanine ， perylene, quinacridone; Azo class pigment, other has the compound of high score subclass of the functional group of sulfonic group, carboxyl, quaternary ammonium salt etc.

As external additive, can preferably use inorganic particles.As the concrete example of inorganic particles, for example can enumerate silica, aluminum oxide, titanium oxide, barium titanate, magnesium titanate, calcium titanate; Strontium titanate, zinc oxide, White tin oxide, silica sand, clay, mica, wollastonite; Zeyssatite, chromic oxide, cerium oxide, red iron oxide (ペ Application ガ ラ), ANTIMONY TRIOXIDE SB 203 99.8 PCT, Natural manganese dioxide; Zirconium white, permanent white, barium carbonate, lime carbonate, silit, silicon nitride etc.

In addition; The polymer based fine particles; For example can the give an example PS, methacrylic ester or the Yodo Sol GH 28 that obtain through not soapy letex polymerization or suspension polymerization, dispersion polymerization or organosilicon, benzoguanamine; The polycondensation class of nylon etc. is through the polymer particle of heat-curing resin.Such flowing agent carries out surface treatment, improves hydrophobicity, even under high humidity, also can prevent the deterioration of flow characteristics or charged characteristic.For example can enumerate silane coupling agent, the silylation agent has the silane coupling agent of fluoro-alkyl, organic titanate class coupling agent, the coupling agent of aluminium class, silicone oil, modified silicon oil etc.

As magnetic carrier, can use iron powder, ferrite powder, magnetic iron powder, magnetic resin carriers etc. are in the past with regard to known material.In addition,, can be amino resin, urea-formaldehyde resins for example, melmac, benzoguanamine resin, urea resin, polyamide resin etc. as coating material.

As conducting powder, can use metal powder, carbon black, titanium oxide, White tin oxide, zinc oxide etc.

And in the fluid of the method for manufacture of above-mentioned resin particle, also can use the fluid that contains Nano silver grain to implement.Thus, can make Nano silver grain in resin structure homodisperse, can make the resin particle that contains silver-colored particulate, can give rosin products with antibacterial effect.

Like this, can make volume average particle size 1～10000nm, preferred 10～800nm, the more preferably dispersion liquid of the resin particle of 40～500nm (suspension-s).

And, as stated, remove the 1st d1 of importing portion, beyond the 2nd d2 of importing portion, the 3rd d3 of importing portion can be set on treatment unit also, under this situation, for example can be from each importing portion, solution, surfactant soln, the tinting material of resin imported in the treatment unit respectively.Like this, but each manages concentration, the pressure of each solution, can more critically control the reaction that resin particle generates.Even under the situation that is provided with the importing portion more than the 4th, the fluid sectionalization that equally also can be so will import to treatment unit.

Below, describe in more detail for disclosed embodiment of the present invention.But the present invention has more than and is defined in these embodiment.

Use as Fig. 1 (A) shown in, can be near the reaction unit that evenly mixes in the film fluid of subtend processing that set, that at least one side is rotated with respect to the opposing party with face 1, formation between 2 each other discretely; With resin formation solution or water dispersion; It is collaborated with aqueous vehicles in the film fluid, make its uniform mixing.

What explain is; In following embodiment; So-called " from central authorities "; Refer to such an extent that be the meaning of " from the 1st d1 of importing portion " of treatment unit shown in above-mentioned, Fig. 1 (A), the 1st fluid is meant that the above-mentioned the 1st is processed liquid, that the 2nd fluid is meant is above-mentioned, treatment unit shown in Fig. 1 (A) " that import from the 2nd d2 of importing portion, above-mentioned the 2nd is processed liquid.In addition, here " part " is " weight part ".

(volume average particle size)

Size-grade distribution uses the particle size distribution device (the trade(brand)name microtrac UPA150 of day machine dress strain (strain) system) of having used laser Doppler method to measure, and adopts volume average particle size.

(embodiment K1)

In that being installed, stirrer, distillation tower, temperature take into account in 4 mouthfuls of flasks of glass of nitrogen ingress pipe, with the ratio charging of NSC 6366 8mol, terepthaloyl moietie 4mol, terephthalic acid 8mol.In mantle heater (mantle heater), under nitrogen gas stream, it is warming up to 180 ℃; Add 0.14% polymerization starter (titanium tetrabutoxide) therein with total charge with respect to acid and pure composition; Through heating, make its reaction thus while stirring.The carrying out of reaction followed the trail of through measuring acid number, finishes reaction in the moment of the acid number that has reached regulation, obtains weight average molecular weight and be 650, Tg is that 56 ℃, Tm are that 103 ℃, acid number are 3.2 vibrin.

On one side will be as the 1st fluidic aqueous vehicles (1% lauryl sodium sulfate aqueous solution) from central authorities; Carry out liquor charging with supply pressure/back pressure=0.20MPa/0.01Mpa, rotating speed 500rpm; The 5% vibrin ethyl acetate solution that will use above-mentioned vibrin on one side is as the 2nd fluid; Flow with 10ml/min imports processing with face 1, between 2, and delivery flow is mixed with the mode of 30g/min.Obtaining volume average particle size is the vibrin microparticle dispersion of 45.2nm.

(embodiment K2～K4)

Embodiment K2～K4 uses vibrin ethyl acetate solution and the aqueous vehicles identical with embodiment K1, changes rotating speed, supply pressure, delivery flow and obtains the vibrin microparticle dispersion.

(embodiment K5)

On one side will be as the 1st fluidic aqueous vehicles (1% lauryl sodium sulfate aqueous solution/0.5% polyvinyl alcohol water solution) from central authorities; Carry out liquor charging with supply pressure/back pressure=0.60MPa/0.45Mpa, rotating speed 500rpm; On one side with vibrin (weight average molecular weight 16; 000, softening temperature=105 ℃) 210g mixes (what explain is, should " mixings " be not equivalent to former " ready-mixed ") in ion exchanged water 490g; Heat to 150 ℃ before this polyester resin aqueous dispersion will be imported; Make the softening back of resin (30% softening polyester resin aqueous dispersion), should soften polyester resin aqueous dispersion, import with 10ml/min and handle with face 1, between 2 as the 2nd fluid.Obtaining volume average particle size is the vibrin microparticle dispersion of 63.1nm.

(embodiment K6～K8)

For embodiment K6～K8, use with the same ion exchanged water of embodiment K5 in the vibrin (softening polyester resin aqueous dispersion) and the aqueous vehicles that have been softened, change rotating speed, supply pressure, delivery flow and obtain the vibrin microparticle dispersion.

(embodiment K9)

On one side will be as the 1st fluidic aqueous vehicles (0.7% aerosol OT (trade(brand)name: AOT from central authorities; With the pure medicine of light society system)/deionized water 99.3% solution); Carry out liquor charging with supply pressure/back pressure=0.15MPa/0.01Mpa, rotating speed 1000rpm; One side as the 2nd fluid, imports processing with face 1,2 between with 10ml/min with 0.4% PS (PS) (trade(brand)name: Poly vinylbenzene, Ardrich society system)/THF (THF) 99.6% solution (also being referred to as " PS solution "); The mode that with the delivery flow is 20g/min is carried out mixing and emulsifying, and obtaining volume average particle size is the polystyrene resin microparticle dispersion of 58.3nm.

(embodiment K10～K12)

For embodiment K10～K12, use PS solution and the aqueous vehicles identical with embodiment K9, change rotating speed, supply pressure, delivery flow and obtain the polystyrene resin microparticle dispersion.

(comparative example K1)

Use vibrin ethyl acetate solution and the aqueous vehicles identical, use ClearMix (M technology society system) that above-mentioned vibrin ethyl acetate solution is suspended in above-mentioned aqueous vehicles, form the vibrin microparticle dispersion with embodiment K1.This moment, the rotating speed of ClearMix was 20000rpm, carried out stirring in 30 minutes.Having obtained volume average particle size is the vibrin particle dispersion liquid of 105.4nm.

The above results is shown in table 21 (what explain is that embodiment 1～12 in the table and comparative example 1 are represented the foregoing description K1～K12 and comparative example K1 respectively).

[table 21]

In order to obtain resin particle energy needed amount, compare with comparative example, though the volume average particle size of embodiments of the invention side diminishes, all be below 1/10th.Hence one can see that, and the energy efficiency of the method for manufacture of the foregoing description is excellent.

(L) emulsion

Below, the operation that is used to obtain emulsion is described.

Particularly, between the processing that can be rotated with respect to the opposing party with face, at least one side near isolating processing that sets for subtend is with face, with the liquid of formation external phase as the 1st fluid; The liquid that forms disperse phase as the 2nd fluid, to keep independently state, is fed each fluid corresponding to each fluidic independent paths; Import and handle with between the face; Form the film fluid, mix each fluid therein, obtain having the emulsion particle of desirable particle diameter therefrom.At above-mentioned the 1st fluid is under the situation of water, mixed as disperse phase as the 2nd fluid of oil phase at the aqueous phase as external phase, forms the dispersion liquid of O/W shape, from above-mentioned processing with being removed between the face.In addition, be under the situation of oil phase at above-mentioned the 1st fluid, the 2nd fluid is a water, forms the dispersion liquid of W/O shape, from above-mentioned processing with being removed between the face.

Here employed disperse phase liquid can be the dispersed liquid of droplet-like, and external phase liquid is the solution that surrounds by around the formed drop of disperse phase liquid.Thereby, form the liquid of disperse phase and the liquid of formation external phase, as long as it is mutually immiscible liquid, it is not done special qualification.For example, external phase or disperse phase are under the situation of water (water, ethanol, buffered soln and mixed solution thereof etc.), and the opposing party is insoluble organic phase (oil phase) in water in fact.In addition, in the present invention, also can follow mutually to change.

In addition, disperse phase liquid also can be solid paste liquids such as containing particulate, also can be the mixed solution that is formed by various liquid.Particularly; Solid paste liquid containing particulate etc. is used under the situation of the 1st fluid as disperse phase; Even exist in particulate in the pulpous state and the liquid under the situation of difference in specific gravity; Can through between handling, collaborate with the 2nd fluid with face, emulsion formization, suppress separating of the 1st fluidic particulate and liquid, efficient is fetched particulate well.This is because owing to handle and to be small stream between use face, so the influence that produces of gravity and the influence of surface tension or the viscous force cause of comparing and diminishing.

In addition; In order to obtain having the emulsion of volume granularity more uniformly; Preferably in the 1st fluid or the 2nd fluid or each fluidic two sides, add the dispersion agent of nonionogenic tenside or cats product, AS, amphoterics etc.As nonionogenic tenside or cats product, AS, amphoterics; Need only the tensio-active agent that carries out coordination on the emulsion particle surface, makes the emulsion particle stabilization in the disperse phase, just it is not done special qualification.

Between the treated side of supply with pressing and being rotated through the fluidic pressure equilibrium of applied pressure and will the 1st fluid and the 2nd fluid collaborate with face 1, between 2, in the film fluid apart from the processing of having controlled; The 1st fluid and the 2nd fluid are mixed in this film fluid, form emulsion.

Because in the film fluid, carrying out each fluidic mixes; Do not use uneven preparation to disperse modulator; Therefore directly modulate, often produce uniform mixing field, can easily obtain coefficient of variation as the volume granularity in the size distribution of purpose and be 0.3～30% emulsion.Here calculate with following formula for coefficient of variation.

[several 1]

Coefficient of variation C.V. (%)=(standard deviation S TD./volume average particle size d) * 100

In addition, volume average particle size in the following formula and standard deviation calculate with two following formulas.What explain is, said here standard deviation is the distribution density target of the size-grade distribution measured, and does not mean that the standard deviation (error of statistics) on the statistics.

[several 2]

Volume average particle size $d=\frac{\mathrm{\&Sigma;}\left(d_i{V}_i\right)}{\mathrm{\&Sigma;}{V}_i}$

From the little arrangement of particle diameter, has d ₁, d ₂... d _i... d _kThe particle of particle diameter be respectively n ₁, n ₂... n _i... n _kIndividual, the volume of per 1 particle is V _i

[several 3]

Standard deviation S TD.=(d84%-d16%)/2

In addition, state is imported into processing with face 1, between 2 to each fluid to keep independently, therefore can in the film fluid that forms, each fluid be mixed, so can omit previously necessary ready-mixed operation.Thus, availablely obtain desirable emulsion than also low in the past energy.

Because need not carry out the ready-mixed of external phase and disperse phase, therefore do not produce uneven stuff and other stuff, can evenly drop into energy, so can make the emulsion that had uniform volume granularity than comparing in the past.In addition, handle the interval of handling with portion 20, may command particle size of emulsion through free adjustment the 1st with portion 10 and the 2nd.In addition; The particle size of emulsion that obtains, except that the interval of handling with face 1,2, also can be through viscosity, the surface tension of external phase and disperse phase; The liquor charging speed of these liquid, handle with the various conditions of the rotating speed of face etc. and control, can set as required aptly.

Need to prove that the appellation of the 1st, the 2nd in said each fluid is that the fluidic n of a plurality of existence of expression is individual here, just also can there be the fluid more than the 3rd in the mark in order to discern.If use the fluid more than the 3rd, when the manufacturing of composite emulsion or in disperse phase, to make under the situation of multiple emulsion be useful.

In addition; When the manufacturing of emulsion; Can be for example; Adopt drawdown pump Q shown in Figure 18 (A) suchly, with the 1st handle with portion 10 and the 2nd handle with portion 20 outsides, promptly be processed stream that liquid passes through become decompression state (comprising vacuum state) on every side, can deposit gas, lower boiling organic solvent, steam etc. such as oxygen to the air that is processed in the liquid to be contained in the emulsion chemical industry preface or molten and outgas or desolventizing.Like this,, discharge with atomize with face from handling owing between handling, mixing the emulsion that obtains with face, so this fluidic surface-area increase, the very high advantage of degassing desolventizing efficient had.

Contain in the moity under the situation of material of easy oxidation of unsaturated fatty acids etc., for anti-oxidation, preferably between handling with face the such inert gasses of importing nitrogen or argon gas, in this environment, handle.For example, the 1st processing is handled with portion 20 outsides, promptly is processed liquid through being full of with above-mentioned rare gas element around the stream with portion 10 and the 2nd.

The emulsion that obtains through the present invention, for example, can in following purposes etc., use: toning agent thermal expansion agent pressure-sensitive copy paper electrothermal sensitive recording paper, spacer, HSLC be with the weighting agent of post, the piezometry film; Thermal medium, dimming glass, thermo-color (temperature-sensitive liquid crystal, temperature-sensitive dyestuff), magnetism swimming capsule, agricultural chemicals; Artificial diet, synthetic seed, perfume compound, spices, cream and washing lotion; Lipstick, the vitamins capsule, gac contains the enzyme capsule, DDS (drug delivery system).

Like this, the method for manufacture of emulsion of the present invention, the coefficient of variation that can easily obtain the volume granularity in the size distribution is 0.3～30% emulsion, can obtain the particle of single stably dispersing.And, do not need indispensable in the past preparation dispersion step, and then often produce new mixing field, and can get rid of the unequal thermal history in the preparation dispersion state, the influence of the unequal energy amount of casting, so can obtain uniform particle diameter.In addition, handle the interval of handling with portion 20, therefore can freely control particle diameter with portion 10 and the 2nd owing to can freely regulate the 1st easily.Thus, can simplify flow chart, compare with former method, can obtain desirable particle at short notice, energy efficiency is good, and productivity is good.

Below, describe in more detail for disclosed embodiment of the present invention.But the present invention has more than and is defined in these embodiment.

In following embodiment; So-called " from central authorities "; Refer to such an extent that be the meaning of " from the 1st d1 of importing portion " of treatment unit shown in above-mentioned, Fig. 1 (A); The 1st fluid is meant that the above-mentioned the 1st is processed liquid, that the 2nd fluid is meant is above-mentioned, treatment unit shown in Fig. 1 (A) " that import from the 2nd d2 of importing portion, above-mentioned the 2nd is processed liquid.In addition, calculate according to above-mentioned illustrated that kind for coefficient of variation.

(embodiment L1)

On one side will be as the 1st fluidic 2%Tween80 aqueous solution from central authorities; Carry out liquor charging with supply pressure/back pressure=0.1MPa/0.05Mpa, rotating speed 10000rpm; To import the 1st processing as the 2nd fluidic whiteruss on one side and handle with between the face 2 with face 1 and the 2nd, liquid effluent mixes with the mode of 5.7ml/min.What explain is, is that 2% ground of whole outputs carries out liquor charging to the 2nd fluid with whiteruss.Obtain emulsion shown in Figure 40.Handle back solution, use with the laser diffraction and scattering method and measure as the particle size distribution device (SIMAZU goods, trade(brand)name SALD-7000) of measuring principle, volume average particle size is 2.42 μ m as a result, and the CV value is 2.8%.

(embodiment L2)

On one side will be as the 1st fluidic 2%Tween80 aqueous solution from central authorities; Carry out liquor charging with supply pressure/back pressure=0.1MPa/0.02Mpa, rotating speed 10000rpm; To import the 1st processing as the 2nd fluidic whiteruss on one side and handle with between the face 2 with face 1 and the 2nd, liquid effluent mixes with the mode of 10.4ml/min.What explain is, is that 2% ground of whole outputs carries out liquor charging to the 2nd fluid with whiteruss.Obtain emulsion shown in Figure 41.Handle back solution, use with the laser diffraction and scattering method and measure as the particle size distribution device (SIMAZU goods, trade(brand)name SALD-7000) of measuring principle, volume average particle size is 11.07 μ m as a result, and the CV value is 0.58%.

(embodiment L3)

On one side will be as the 1st fluidic 2%Tween80 aqueous solution from central authorities; Carry out liquor charging with supply pressure/back pressure=0.1MPa/0.10Mpa, rotating speed 10000rpm; To import the 1st processing as the 2nd fluidic whiteruss on one side and handle with between the face 2 with face 1 and the 2nd, liquid effluent mixes with the mode of 2.6ml/min.What explain is, is that 2% ground of whole outputs carries out liquor charging to the 2nd fluid with whiteruss.Handle back solution, use with dynamic light scattering method and measure as the particle size distribution device (day machine dress (strain) goods, trade(brand)name microtrac UPA-150) of measuring principle, volume average particle size is 0.36 μ m as a result, and the CV value is 28.6%.

(comparative example L1)

In 2%Tween80 aqueous solution 294ml, add whiteruss 6ml, handle 10min with 20000rpm with ClearMix (M technology society system).Handle back solution, use with the laser diffraction and scattering method and measure as the particle size distribution device (SIMAZU goods, trade(brand)name SALD-7000) of measuring principle, volume average particle size is 6.64 μ m as a result, and the CV value is 34.6%.

(casting rate) for energy

For embodiment L1～L3 and comparative example L1, energy is cast rate and is illustrated in (what explain is that embodiment 1～3 in the table and comparative example 1 are represented the foregoing description L1～L3 and comparative example L1 respectively) in the table 22.

[table 22]

	Embodiment 1	Embodiment 2	Embodiment 3	Comparative example 1
					Rotating speed [rpm]	10000	10000	10000	20000
Particle diameter D50 [μ m]	2.42	11.07	0.36	6.64
					Coefficient of variation [%]	2.8	0.58	28.6	34.6
Energy is cast rate [-]	0.38	0.12	0.57	1

Thus, compare with comparative example, embodiment, not only the CV value is little, and it is about half point-1/10th with respect to comparative example that the energy of embodiment is cast rate.Show thus, but method of manufacture of the present invention is an emulsion particle low-yield, the high manufacturing objective size of efficient.

(for emulsion particle through the time change)

For embodiment L1～L3 and comparative example L1; Volume average particle size after the processing and CV value and after 1 day and the volume average particle size after 7 days and CV value representation (what explain is in table 23; Embodiment 1～3 in the table and comparative example 1 are represented the foregoing description L1～L3 and comparative example L1 respectively).

[table 23]

Can know that with respect to comparative example, the emulsion of embodiment does not change through behind the certain hour yet.For comparative example, after 7 days, water separates with oil phase fully.Learn that thus the emulsion particle storage stability that the method for manufacture through emulsion of the present invention obtains is good.

What (M) temperature variation produced separates out

Below, for the reaction that generates particulate of separating out that produces because of temperature variation, be that example describes with the acyclovir.

Acyclovir (general name: JAN; INN) [chemical name: 9-[(2-hydroxyl-oxethyl) methyl] guanine] for having the antivirus action medicine of purine skeleton, is as hsv and the caused infection of varicella zoster virus disease; Promptly; Lower immune function patient (malignant tumour oneself Immunological diseases etc.) the herpes simplex varicella zoster of having fallen ill, the therapeutical agent of encephalitis meningitis etc. is by the compound of clinical use widely.Low (about 0.001w/v%～0.01w/v%), through heating to more than 70 ℃, its solubleness increases acyclovir, can reach about 8w/v% to the solubleness of the water of normal temperature.

This reaction, as Fig. 1 (A) shown device, can near discretely each other subtend set, at least one side with respect to the processing of the opposing party's rotation with face 1, between 2, on one side one side uniform mixing takes place by the strong hand.

At first; From the 1st d1 of importing portion as 1 stream; To use fluid as the cooling that the 1st fluidic contains the aqueous vehicles lower than following the 2nd fluidic temperature; Importing can near discretely each other at least one side of subtend configuration with respect to the processing of the opposing party's rotation with 1,2 in face, the film fluid that generation is made up of the 1st fluid between this processing is with face.

Then, from the 2nd d2 of importing portion as other stream, will be as the 2nd fluidic, contain a kind of heating at least and dissolved the fluid of the solution of acyclovir to 85 ℃ the water, directly import the above-mentioned film fluid that constitutes by the 1st fluid.

As stated, in the film fluid of processing with face 1, formation between 2 of the pressure equilibrium of applied pressure between the processing of supply with pressing and being rotated through fluidic is with face and controlled distances, the 1st fluid and the 2nd fluid collaborate.In this film fluid, the 1st fluid and the 2nd fluid are mixed, are discontented with 70 ℃ through the temperature of the 1st fluid and the 2nd fluidic mixed solution, and in this mixed solution, the original contained acyclovir that has is separated out in the 2nd fluid.More specifically, handle with face 1, the temperature of acyclovir solution between 2, make the solubleness decline of acyclovir, the acyclovir particulate is separated out water through being reduced in.Through at least one side with respect to the processing of the opposing party rotation with face 1,2; Handling with face 1, film fluid between 2 by the strong hand by uniform mixing; Can between the 1st fluid and the 2nd fluid, not form the interface and cause it not mix well, make that to reduce the solubility change that causes by above-mentioned temperature rapid.

What explain is, owing to can carry out above-mentioned reaction (evolution reaction) with face 1, between 2 and get final product handling, therefore, also can import the 2nd fluid from the 1st d1 of importing portion on the contrary with above-mentioned, imports the 1st fluid from the 2nd d2 of importing portion.That is, the appellation of the what is called the 1st, the 2nd in each fluid is that the fluidic n of a plurality of existence of expression is individual, and just also can there be the fluid more than the 3rd in the mark in order to discern.

In addition, also can in the 1st fluid and the 2nd fluidic two sides, contain identical particulate starting material.

The particle diameter of the particulate that obtains, single dispersity, or the control of crystal type can be through change handling with the rotating speed of face 1,2 or processing with face 1, distance and film flow rate of fluid or temperature between 2, and perhaps material concentration etc. is regulated.

As the particulate starting material that is used beyond the acyclovir,, just it is not done special the qualification if the solubleness of solution is changed along with temperature.This time, solubleness is with respect to the curve (solubility curve) of temperature, can be that solubleness rises along with temperature and under the situation about rising, and also can be as rising along with temperature with respect to the calcium hydroxide of water or the such solubleness of cesium sulfate the enforcement of getting off of the situation of decline.And, also can become the enforcement of getting off of maximum situation in specified temp (under this situation being 34.38 ℃) solubleness in this wise like sodium sulfate.Though under the situation of above-mentioned acyclovir, imported cooling with fluid as the 2nd fluid,, under the such situation of calcium hydroxide or cesium sulfate, can import and heat with fluid as the 2nd fluid.Under the such situation of sodium sulfate, be boundary with the specified temp, can separately use cooling with fluid and heat and use fluid.

In addition, the solvent of use is also the same with above-mentioned particulate starting material, it is not done special the qualification.Also can make water, ion exchanged water, ultrapure water, acid, alkaline aqueous vehicles, methyl alcohol or ethanol, the organic solvent of toluene etc.In addition, contain the grease of silicone oil or unsaturated fatty acids, sunflower oil, or the such oil of industrial gear oil.

In addition, also can not use as stated in order to handle with face 1, the above-mentioned cooling of cooling off between 2, heating with fluid or heat and implement with fluid with the temperature regulation of fluid etc.Under this situation; Can the 1st handle with portion 10 and the 2nd processing and be provided with thermoregulative mechanism (temperature adjustment mechanism) J1 with at least one of portion 20; J2; The particulate starting material solution that solubleness is changed along with temperature variation with above-mentioned thermoregulative mechanism directly to handling with carrying out temperature adjustment between face, processing with face 1, particulate is separated out.

This temperature adjusting structure is not done special qualification, is being cooled under the situation of purpose, with portion 10,20 cooling end is set in processing.Particularly, on handling, install with portion 10,20 can through as temperature adjustment with the frozen water of medium or the pipe arrangement of various heat-eliminating mediums, or cooling module (peltiert element) etc., electric or chemically form the cooling element of cooling effect.

Be heated to be under the situation of purpose, with portion 10,20 heating part be set in processing.Particularly, handle with portion's 10,20 installations through as temperature adjustment with the steam of medium or the pipe arrangement of the various media of heating, or electricity such as electric heater or chemically form the Heating element of heating functioin.

In addition, also can be provided with in the annulus resettlement section can with handle the resettlement section that the new temperature control medium that directly joins with portion is used.Thus, available processes is carried out temperature adjustment to handling with face with the thermal conduction of portion.In addition, handle with cooling element in the portion 10,20 and Heating element energising being embedded in, or bury underground the changes in temperature matchmaker through with path at this path through temperature adjustment with medium (changes in temperature matchmaker), carry out temperature adjustment from the inboard to processing with face thus.What explain is, temperature adjusting structure J1 shown in Figure 25, and J2 is the one of which example, is to manage throughout to pass through the pipe arrangement (big envelope) of temperature adjustment with medium with the set inside of portion 10,20.

In addition, also can all be immersed in temperature adjustment with implementing in the fluid with portion 10,20 with handling.For example, will handle with portion 10,20 being housed in the container, and in this container, import temperature adjustment and use fluid, thus directly to handling with portion and handling with carrying out temperature adjustment between face.

And, such mechanism, though use as the 2nd fluid temperature adjustment with the fluidic situation under also can and usefulness.

In addition, also can containing tensio-active agent among either party at least and implement at the 1st above-mentioned fluid or the 2nd fluid etc., mixing solutions.

As the tensio-active agent that uses; Can be known tensio-active agent; Also can be new synthetic tensio-active agent, do not do special qualification, can use to solution have good solubility, simultaneously can be with the particulate of separating out various tensio-active agents of dispersive well in solution.Can enumerate various cationic surfactants or anionic surfactant or nonionic surfactant, X 2073, dodecyl phenenyl sulfate; Trombovar, pentadecyl sodium sulfate, sodium octyl sulfate; Sodium oleate, sodium laurate, StNa; Calcium stearate, sucrose fatty ester, Tween20 and Tween80 (this can obtain, be the polyoxyethylene sorbitan fatty acid esters class from ICI Specialty Chemicals); Vinylpyrrolidone polymer, tyloxapol (tyloxapol), Pluronic F68 and F108 (this can obtain from BASF, be the segmented copolymer of oxyethane and propylene oxide); Tetronic 908 (T908) (this can obtain from BASF, for from oxyethane and propylene oxide 4 functionality segmented copolymers) to the continuous affixture of quadrol; VISOSE, Yelkin TTS, aerosol (Aerosol) OT (this can obtain, be the dioctyl ester of sodium sulfo-succinate from American Cyanamid); Duponol P (this can obtain, be Sodium Lauryl Sulphate BP/USP from DuPont); Triton X-200 (this can obtain, for alkyl aryl polyether sulfonate) from Rohm and Haas, Carbowax 3350 and 934 (this can obtain, be polyethylene glycols), Crodesta F-110 (this can obtain, be the mixture of sucrose stearate and sucrose distearate) from Croda Inc. from Union Carbide; Crodesta 5L-40 (this can obtain from Croda Inc.), (this is C to reach SA90HCO ₁₈H ₃₇CH ₂-(CON (CH ₃) CH ₂(CHOH) ₄CH ₂OH) ₂) etc.Also can separately use according to the particulate of purpose.

And, can heat (heating) and handle with between face, or between handling with face irradiation ultraviolet radiation (UV), between processing is with face, give ultrasonic energy in addition.Particularly, handle with face 1 and the 2nd processing to be provided with under the situation of temperature head the 1st, can in the film fluid, convection current take place, so have and to promote the advantage of reacting thus with face 2.

More specifically, for heating (heating), also as above-mentioned explained, for example, well heater and the big envelope through thermal medium are set through managing at least one side with portion 10,20 throughout, can heat (heating) film fluid.In addition, for irradiation ultraviolet radiation (UV), for example, reason can be used in the face of film fluid irradiation ultraviolet radiation (UV) from corresponding processing with the elements such as lamp that at least one side of portion 10,20 is provided with irradiation ultraviolet radiation throughout.In addition, for supplying with ultrasonic energy, for example, at least one side that can manage throughout with portion 10,20 is provided with ultrasonic oscillator.

In addition; Through with above-mentioned evolution reaction can guarantee to reduce pressure or the container of vacuum state in carry out, make at least and handle 2 sides that the back fluid is discharged from and become decompression or vacuum state; React the degassing of the gas that is contained in the gas that taken place and the above-mentioned fluid, or above-mentioned fluidic desolventizing.Thus; Even with separate out processing and almost carry out simultaneously containing the fluid of the particulate of between handling, being separated out under the situation that desolventizing handles with face, discharge with atomize with face from processing; Therefore this fluidic surface-area increases, and has the very high advantage of desolventizing efficient.Therefore than simply, 1 operation is carried out particulate and is made and handle and the desolventizing processing in fact with contact.

Like this, can make average primary particle diameter is 0.5～10000nm, is preferably 1～500nm, and more preferably the particulate of 10～200nm is by dispersed suspension-s.And, in containing the solution of particulate starting material, added under the situation of above-mentioned tensio-active agent, can make be dispersed with on the surface dispersion agent by coordination the suspension-s of particulate, it is very good that the redispersibility of the particulate that obtains becomes.In addition, impurity is sneaked into and is lacked in manufacturing process, under the situation that crystallization is separated out, can highly control its crystallization degree.

In addition, as stated, also can remove the 1st d1 of importing portion, beyond the 2nd d2 of importing portion, the 3rd d3 of importing portion is set on treatment unit.Under this situation, for example from each importing portion, can fluid be used in temperature adjustment, contained the solution of particulate starting material, tensio-active agent imports in the treatment unit respectively.Like this, but each manages concentration, the pressure of each solution, can more critically control the reaction that particulate generates.Even under the situation that is provided with the importing portion more than the 4th, the fluid sectionalization that equally also can be so will import to treatment unit.

Below, explain in more detail that for disclosed embodiment of the present invention still, the present invention has more than and is defined in these embodiment.

What explain is; In following embodiment; So-called " from central authorities "; Refer to such an extent that be the meaning of " from the 1st d1 of importing portion " of treatment unit shown in above-mentioned, Fig. 1 (A), the 1st fluid is meant that the above-mentioned the 1st is processed liquid, that the 2nd fluid is meant is above-mentioned, treatment unit shown in Fig. 1 (A) " that import from the 2nd d2 of importing portion, above-mentioned the 2nd is processed liquid.

Shown in Fig. 1 (A); Have that subtend sets can near isolating processing with face, at least one side with respect to the processing of the opposing party's rotation with face 1, the film fluid that forms between 2 in the reaction that evenly mixes of use adorn; 85 ℃ the acyclovir aqueous solution is cooled off in the film fluid, carry out separating out of acyclovir.

(embodiment M1)

To carry out liquor charging for 15 ℃ with supply pressure/back pressure=0.15MPa/0.01Mpa, rotating speed 500rpm, liquor charging temperature as the 1st fluidic 5%Tween80 aqueous solution from central authorities; Will be as 85 ℃ of the 2nd fluidic, the 3% acyclovir aqueous solution imports processing with between face with 10ml/min.The 1st fluid and the 2nd fluid are mixed in the film fluid, and acyclovir microparticulate solution is discharged from face from handling.The temperature of liquid effluent is 48 ℃.

The size-grade distribution of acyclovir particulate uses the particle size distribution device (day machine dress (strain) goods, trade(brand)name microtrac UPA150) of having used laser Doppler method to measure, and volume average particle size is 88.6nm as a result.

And; The Powdered acyclovir particulate that this acyclovir dispersion soln vacuum lyophilization obtains is put in the ion exchanged water once more, stirred with high-speed stirring type dispersion machine (trade(brand)name: ClearMix, M technology society system); The result obtains the acyclovir microparticle dispersion once more; Identical before volume average particle size and the vacuum lyophilization, be 88.1nm, the redispersibility of the acyclovir particulate powder of confirming to obtain is good.

For embodiment M2～M4, use the Tween80 aqueous solution and the acyclovir aqueous solution identical with embodiment M1, change rotating speed, supply pressure, back pressure, obtain acyclovir microparticle dispersion and acyclovir powder.

(comparative example M1)

Stir the 4%Tween80/2% acyclovir aqueous solution on one side, Yi Bian heat to 85 ℃ the dissolving acyclovir.Then, use ClearMix (M technology society system),, to form the acyclovir microparticle dispersion Yi Bian be cooled to 48 ℃ Yi Bian stir this solution.At this moment, the rotating speed of ClearMix carries out with 20000rpm.Having obtained volume average particle size is the acyclovir particle dispersion liquid of 1340nm.In addition, likewise confirm as redispersibility with embodiment, still, particle diameter is 3800nm behind the redispersion, and compares strong aggegation before the vacuum lyophilization.

Above-mentioned result is illustrated in (what explain is that embodiment 1～4 in the table and comparative example 1 are represented the foregoing description M1～M4 and comparative example M1 respectively) in the table 24.

[table 24]

Casting rate in order to make acyclovir particulate energy needed, compare with comparative example, is about 1/200th at embodiments of the invention M1, and embodiment M2, M3 are about 1/24th, and embodiment M4 is about 1/3rd.Hence one can see that, and the modulator approach of embodiment not only can be made the particle more small than comparative example, and energy efficiency is excellent.

Above-mentioned result is illustrated in (embodiment 1～4 and comparative example 1 in the table are represented the foregoing description M1～M4 and comparative example M1 respectively) in the table 25.

[table 25]

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Comparative example
						Rotating speed [rpm]	500	1000	1000	2000	21500
Particle diameter D50 [nm]	88.6	74.3	101.5	64.1	1340
						Energy is cast rate [-]	0.005	0.041	0.041	0.330	1

(N) separating out through organic reaction

Below, to generating the reaction of particulate through separating out of organic reaction, be that example describes with the reaction of Succinic Acid two fat and nitrile.

From the 1st d1 of importing portion as 1 stream, will as the 1st fluidic contain at least a kind of in the presence of highly basic lysed mode be expressed as R ₁The nitrile of-CN or be expressed as R ₂The fluid of the nitrile of-CN or the mixture of these nitriles, importing can near discretely each other at least one side of subtend configuration with respect to the processing of the opposing party's rotation with face 1, between 2, the film fluid that generation is made up of the 1st fluid between this processing is with face.

In the formula under the situation of the reaction of above-mentioned Succinic Acid two fat and nitrile, R ₁And R ₂Identical or different, be respectively the homocyclic ring or the hetero ring type aromatic series base that do not replace or be substituted.Preferred homoatomic ring type aromatic series base R ₁And R ₂Base, for monocycle to or 4 ring types, in particular for the group of monocyclic or 4 ring types, for example be phenyl, xenyl and naphthyl.Preferred hetero ring type aromatic series base R ₁And R ₂Base is monocyclic to 3 ring type, and, can have the fused benzene rings more than 1.Above-mentioned cyanic acid not only can be on heterocycle, also can be on homocyclic ring.Instance as heterocyclic radical can be pyridyl, pyrimidyl, pyrazinyl; Triazinyl, furyl, pyrryl, thio-phenyl; Quinolyl, tonka bean camphor base, benzofuryl, benzimidazolyl-; Benzo azoles base, dibenzofuran group, benzothienyl, dibenzothiophene; Indyl, carbazyl, pyrazolyl, imidazolyl;

azoles base, different

azoles base, thiazolyl; Indazolyl, benzothiazolyl, pyridazinyl; The cinnolines base, quinazolyl, quinolyl (キ Na ゾ リ Le); Phthalazinyl, phthalazine diketone base (Off タ ラ ジ Application ジ オ ニ Le), phthalyl amido (Off タ Le ア ミ ジ Le); Network ロ モ ニ Le, naphthalene lactin base (Na Off ト ラ Network タ ミ Le), quinoline ketone group (キ ノ ロ ニ Le); Adjacent benzene first sulfimide base (オ Le ト ス Le ホ ベ Application ズ イ ミ ジ Le), dimaleoyl imino (マ レ イ ミ ジ Le), Na Off タ リ ジ ニ Le; Benzoglyoxaline ketone group (ベ Application ズ イ ミ ダ ゾ ロ ニ Le), benzo

oxazolone base (ベ Application ゾ オ キ サ ゾ ロ ニ Le), benzothiazole ketone group (ベ Application ゾ チ ア ゾ ロ ニ Le); ベ Application ゾ チ ア ゾ チ オ ニ Le, quinazoline ketone group (キ Na ゾ ロ ニ Le), キ ノ キ ザ ロ ニ Le; The 2 ketone group, dihydroxy-pyrimidine base (ジ オ キ ソ ピ リ ミ ジ ニ Le); Pyriconyl, isoquinolone base, isoquinolyl; Isothiazolyl, benzisoxa

azoles base, benzisothiazole base; The indazole ketone group, acridine ketone group (ア Network リ De ニ Le), quinazoline diones base (キ Na ゾ リ Application ジ オ ニ Le); Quinoxalinediones base (キ ノ キ ザ リ Application ジ オ ニ Le), benzo

piperazine diketo (ベ Application ゾ オ キ サ ジ Application ジ オ ニ Le), benzo

piperazine ketone group and naphthalimido (Na Off タ Le イ ミ ジ Le).Above-mentioned homoatomic ring type and hetero ring type aromatic series base for example can have following common substituting group.(1) chlorine, the halogen atom of bromine or fluorine atom etc.(2) carbon number 1～18, preferred 1～12, special 1～8, more preferably 1～4 branching or nonbranched alkyl.These alkyl also can be selected from F, OH, CN ,-OCOR ₁₆, OR ₁₇, COOR ₁₆, CONR ₁₇R ₁₈And R ₁₆-O-CONHR ₁₆More than 1, for example 1,2,3,4 or 5 substituting groups replace; R ₁₆Be alkyl, naphthyl for example, benzyl, halogeno-benzyl, phenyl, halogenophenyl, aryl such as alkoxyl phenyl or alkyl phenyl, or heterocyclic radical; R ₁₇And R ₁₈Can be identically, also can be difference, the expression hydrogen or alkyl, this alkyl also can be by cyanic acid, hydroxyl or C ₅～C ₆-naphthenic base, aryl or heteroaryl, particularly phenyl or halogen-, alkyl-or alkoxyl group-be substituted phenyl replace; Or R ₁₇And R ₁₈Be integrally formed with nitrogen-atoms, for example form morpholine, 5 Yuans of piperidines or phthalic imidines etc. or 6 s' heterocycle.Further other possible substituting group on the abovementioned alkyl, it is amino to can be list or dialkylated, naphthyl; Phenyl, halogenophenyl, aryl such as alkyl phenyl or alkoxyl phenyl; And the 2-thienyl, 2-benzo azoles base, 2-[4-morpholinodithio base; The 2-benzimidazolyl-, 6-benzimidazoline ketone group, 2-; 3-or 4-pyridyl, 2-, heteroaromatic bases such as 4-or 6-quinolyl.Alkyl has the first meaning that mentions that rises of (2).As not replacing and the instance of substituted alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec.-butyl; The tertiary butyl, tert-pentyl, n-pentyl, n-hexyl, 1,1,3; The 3-tetramethyl butyl, n-heptyl, octane base, nonyl, decyl, undecyl, dodecyl; Methylol, trifluoromethyl, trifluoroethyl, cyano methyl, methoxycarbonyl methyl, acetyl-o-methyl and benzyl etc.(3) alkoxyl group-OR ₁₉R ₁₉Be hydrogen, the alkyl or aryl of above-mentioned definition, C ₅～C ₆-naphthenic base, aralkyl or heterocyclic radical.Preferred R ₁₉Base is a methyl, ethyl, n-propyl, sec.-propyl, trifluoroethyl, phenyl, adjacent-,-or rubigan, adjacent-,-or p-methylphenyl, α-or betanaphthyl, cyclohexyl, benzyl, thienyl or pyranyl methyl.(4)-SR ₁₉Base.R ₁₉Be defined such material in (3).R ₁₉Specific examples methyl is arranged, ethyl, n-propyl, sec.-propyl, phenyl, adjacent-,-or rubigan, adjacent-,-or p-methylphenyl, α-or betanaphthyl, cyclohexyl (cyclohexyl), benzyl, thienyl or pyranyl methyl.(5) cyanic acid.(6) formula-NR ₁₇R ₁₈Base.R ₁₇And R ₁₈Respectively such as in (2) definition.As an example, amino is arranged, methylamino, dimethylamino, ethylamino; Diethylamino, sec.-propyl is amino, the beta-hydroxy ethylamino, the beta-hydroxy propyl group is amino, N; Two (beta-hydroxy ethyl) amino of N-, N, two (beta-cyano ethyl) amino of N-, cyclohexyl is amino, phenyl amino; The N-aminomethyl phenyl is amino, benzylamino, dibenzyl amino, piperidyl or morpholinyl (モ Le ホ リ Le).(7) formula-COOR ₁₆Base.R ₁₆Such as in (2) definition.As an example, methyl is arranged, ethyl, the tertiary butyl, phenyl, adjacent-,-or rubigan, adjacent-,-or p-methylphenyl, or α-or betanaphthyl.(8) formula-COR ₁₉Base.R ₁₉Be defined such material in (3).As an example, methyl is arranged, ethyl, the tertiary butyl, phenyl, adjacent-,-or rubigan, adjacent-,-or p-methylphenyl, or α-or betanaphthyl.(9) formula-NR ₂₀COR ₁₆Base.R ₁₆Such as in (2) definition, R ₂₀Be hydrogen, alkyl, aryl (for example, naphthyl or particularly do not replace or halogen-, alkyl-or-O-alkyl-substituted-phenyl), C ₅～C ₆-naphthenic base, aralkyl or-COR ₁₆, 2 COR ₁₆Also can be integrally formed and form heterocycle with nitrogen-atoms.Alkyl R ₂₀, for example can have and be recited as preferred several carbon atoms in (2).As an example, acetylamino is arranged, propionyl group is amino, and butyryl radicals is amino; Benzoyl-amido, amino to chlorobenzene formacyl, amino to methyl benzoyl; The N-methyl acetyl is amino, and the N-methyl benzoyl is amino, N-succinimide or N phlhalimide.(10) formula-NR ₁₉COOR ₁₆Base.R ₁₉And R ₁₆Be respectively defined such material in (2) or (3).As an example, have-NHCOOCH ₃, NHCOOC ₂H ₂Or NHCOOC ₆H ₅Base.(11) formula-NR ₁₉CONR ₁₇R ₁₈Base.R ₁₉, R ₁₇And R ₁₈Respectively such as in (3) or (2) definition.As an example, urea groups is arranged, N-methyl urea groups, N-phenyl urea groups or N, N '-2 ', 4 '-the 3,5-dimethylphenyl urea groups.(12) formula-NHSO ₂R ₁₆Base.R ₁₆Such as in (2) definition.As an example, there is methane sulfonyl amino, phenyl sulfonyl amino, p-methylphenyl sulfuryl amino or betanaphthyl sulfuryl amino.(13) formula-SO ₂R ₁₆Or-SOR ₁₆Base.R ₁₆Such as in (2) definition.As an example, methyl sulphonyl is arranged, ethylsulfonyl, phenyl sulfonyl, 2-naphthyl alkylsulfonyl, phenyl sulfoxide group (phenylsulfoxidyl).(14) formula-SO ₂OR ₁₆Base.R ₁₆Such as in (2) definition.As R ₁₆Instance, methyl is arranged, ethyl, phenyl, adjacent-,-or rubigan, adjacent-,-or p-methylphenyl, α-or betanaphthyl.(15) formula-CONR ₁₇R ₁₈Base.R ₁₇And R ₁₈Respectively such as in (2) definition.As an example, formamyl is arranged, N-methylamino formyl radical, N-ethylamino formyl radical, N-phenyl amino formyl radical, N, N-formyl-dimethylamino, N-methyl-N-phenyl amino formyl radical, N-Alpha-Naphthyl formamyl or N-piperidyl amino formyl radical.(16) formula-SO ₂NR ₁₇R ₁₈Base.R ₁₇And R ₁₈Respectively such as in (2) definition.As an example, sulfamyl is arranged, N-methyl sulfamyl, N-ethyl sulfamyl, N-phenyl sulfamoyl base, N-methyl-N-phenyl sulfamoyl base or N-morpholinyl sulfamyl.(17) formula-N=N-R ₂₁Base.R ₂₁For the base of coupling key element or do not replace or halogen-, alkyl-or-O-alkyl-substituted-phenyl.The R of alkyl ₂₁, for example, can have in (2) as preferred and carbonatoms record.Instance as R21 can be alpha.-acetylacetanilide, pyrazolyl, and pyriconyl (pyridonyl), adjacent-or p-hydroxybenzene, neighbour-hydroxyl naphthyl, p-aminophenyl or, N-dimethylaminophenyl to N.(18) formula-OCOR ₁₆Base.R ₁₆Such as in (2) definition.As R ₁₆Instance be methyl, ethyl, phenyl, adjacent-,-or rubigan.(19) formula-OCONHR ₁₆Base.R ₁₆Such as in (2) definition.Instance as R16 has methyl, ethyl, phenyl, adjacent-,-or rubigan.In under the situation of the reaction of above-mentioned Succinic Acid two fat and nitrile preferred embodiment in, R ₁And R ₂Be phenyl independently; By 1 or 2 chlorine atoms, 12 methyl, methoxyl group, trifluoromethyl, cyanic acid, methoxycarbonyl, the phenyl that the tertiary butyl, dimethylamino or cyano-phenyl have replaced; Naphthyl; Xenyl; Pyridyl; The pyridyl that has been replaced by pentyloxy; Furyl or thienyl.Particularly, preferred R1 and R2 are respectively phenyl, and 3 or the 4-chloro-phenyl-, 3,5-dichlorophenyl, 4-aminomethyl phenyl; The 4-p-methoxy-phenyl, 3-trifluoromethyl, 4-trifluoromethyl, 3-cyano-phenyl, 4-cyano-phenyl; 4-methoxycarbonyl phenyl, 4-aminomethyl phenyl, 4-tert-butyl-phenyl, 4-dimethylaminophenyl, 4-(to cyano-phenyl) phenyl; 1-or 2-naphthyl, 4-xenyl, 2-pyridyl, 6-pentyloxy-3-pyridyl, 2-furyl or 2-thienyl.

Particularly, the nitrile of preferred following formula.

[Chemical formula 2]

In the above-mentioned formula, R ₂₂, R ₂₃And R ₂₄Be hydrogen independently, fluorine, chlorine, bromine, formamyl, cyanic acid, trifluoromethyl, C ₂～C ₁₃-alkyl-carbamoyl, C ₁～C ₁₂-alkyl, C ₁～C ₁₂-alkoxyl group, C ₁～C ₁₂-alkyl thiol, C ₂～C ₁₃-alkoxy carbonyl, C ₂～C ₁₃-alkanoyl yl is amino, C ₁～C ₁₂-alkyl monosubstituted amino, C ₂～C ₂₄-dialkyl amido, do not replace or halogen-, C ₁～C ₁₂-alkyl-or C ₁～C ₁₂-alkoxyl group-substituted-phenyl, phenyl sulfydryl, phenyloxycarbonyl, phenyl amino formyl radical or benzoyl-amido.Above-mentioned alkyl and phenyl not can be and replace, and can be through halogen C yet ₁～C ₁₂-alkyl or C ₁～C ₁₂-alkoxyl group is substituted, R ₂₂, R ₂₃And R ₂₄In be hydrogen more than 1.

Detailed more, be the nitrile of following formula.

[chemical formula 3]

In the formula, R ₂₅And R ₂₆In a side be hydrogen, chlorine, bromine, C ₁～C ₄-alkyl, cyanic acid, C ₁～C ₄-alkoxyl group does not replace or chloro-, methyl-or C ₁～C ₄-alkoxyl group-substituted-phenyl, formamyl, C ₂～C ₅-alkyl-carbamoyl does not replace or chloro-, methyl-or C ₁～C ₄-alkoxyl group-substituted-phenyl formamyl, the opposing party is a hydrogen.

Employed highly basic under the situation of the reaction of above-mentioned Succinic Acid two fat and nitrile is not done special qualification, but is preferably Lithamide, the alkali amide of sodium amide or potassium amide etc.; Or lithium hydride, the alkalimetal hydride of sodium hydride or potassium hydride KH etc.; Or lithium methoxide, sodium methylate, potassium methylate, lithium ethoxide, sodium ethylate, potassium ethylate; The n-propyl alcohol lithium, n-propyl alcohol sodium, n-propyl alcohol potassium, Virahol lithium, sodium isopropylate, potassium isopropoxide; The propyl carbinol lithium, propyl carbinol sodium, propyl carbinol potassium, sec-butyl alcohol lithium, sec-butyl alcohol sodium; Sec-butyl alcohol potassium, trimethyl carbinol lithium, sodium tert-butoxide, potassium tert.-butoxide, 2-methyl-2-butanols lithium; 2-methyl-2-sodium butylate, 2-methyl-2-butanols potassium, 2-methyl-2-amylalcohol lithium, 2-methyl-2-amylalcohol sodium, 2-methyl-2-amylalcohol potassium; 3-methyl-3-amylalcohol lithium, 3-methyl-3-amylalcohol sodium, 3-methyl-3-amylalcohol potassium, 3-ethyl-3-amylalcohol lithium, 3-ethyl-3-amylalcohol sodium or 3-ethyl-3-amylalcohol potassium etc., particularly by carbonatoms 1～10 primary, the second month in a season or uncle's fatty alcohol deutero-alkali earths or alkali metal alcoholate.Also can use the mixture of above-mentioned alkali.Employed highly basic under the situation of the reaction of above-mentioned Succinic Acid two fat and nitrile is preferably alkali metal alcoholate, and the basic metal under this situation is sodium or potassium in detail, and above-mentioned alcoholate is by the second month in a season or tertiary alcohol deutero-.Therefore, preferred especially highly basic for example, is sodium isopropylate, potassium isopropoxide, sec-butyl alcohol sodium, sec-butyl alcohol potassium, sodium tert-butoxide, potassium tert.-butoxide, sodium tert-amyl alcohol and tertiary amyl alcohol potassium.

In addition, above-mentioned highly basic also can be used in the following fluid that contains Succinic Acid two fat and implements.

Then,, will contain the fluid of at least a Succinic Acid two fat, directly import the above-mentioned film fluid that constitutes by the 1st fluid as the 2nd fluidic from the 2nd d2 of importing portion as other stream.

As Succinic Acid two fat that under the situation of the reaction of above-mentioned Succinic Acid two fat and nitrile, use, it is not done special qualification, can be dialkyl group, diaryl or monoalkyl list aryl ester, wherein succinic acid dialkyl ester and diaryl also can be asymmetric.But, preferably use symmetric Succinic Acid two fat, particularly symmetric succinic acid dialkyl ester.Under the situation that Succinic Acid diaryl ester or monoalkyl list aryl ester exist, aryl is unsubstituted phenyl in detail, or by the halogen as chlorine, methyl, ethyl, sec.-propyl or the C as the tertiary butyl ₁～C ₆-alkyl or methoxyl group or the C as oxyethyl group ₁～C ₆The phenyl that alkoxyl group has replaced.

Under the situation of succinic acid dialkyl ester or monoalkyl list aryl ester, alkyl can be not branching or branching, is preferably branching, preferred carbonatoms 1～18, particularly 1～12, more preferably 1～8, preferred especially 1～5.Branched-alkyl is preferably sec.-propyl, sec.-butyl, the tertiary butyl, the second month in a season or the tertiary alkyl of tert-pentyl or cyclohexyl etc.

Instance as Succinic Acid two fat has methyl-succinate, diethyl succinate, dipropyl succinate, Tabutrex; Diamyl succinate, Succinic Acid dihexyl, diphenyl succinate, dioctyl succinate, diisopropyl ester amber acid; Succinic Acid di-secondary butyl ester, Succinic Acid di tert butyl carbonate, Succinic Acid two tert-pentyl esters, Succinic Acid two-[1, the 1-dimethylbutyl] ester; Succinic Acid two [1,1,3, the 3-tetramethyl butyl] ester, Succinic Acid two [1; 1-dimethyl-amyl group] ester, Succinic Acid two [1-methyl isophthalic acid-ethyl-butyl] ester, Succinic Acid-[1,1-diethylammonium propyl group] ester, diphenyl succinate; Succinic Acid two [4-aminomethyl phenyl] ester, Succinic Acid two [2-aminomethyl phenyl] ester, Succinic Acid two [4-chloro-phenyl-] ester, Succinic Acid list ethyl list phenylester, Succinic Acid two cyclohexyls.Particularly, be preferably diisopropyl ester amber acid.

The highly basic that under the situation of the reaction of above-mentioned Succinic Acid two fat and nitrile, uses and be expressed as R ₁The nitrile of-CN or be expressed as R ₂The nitrile of-CN or the mixture of these nitriles, and Succinic Acid two fat are preferably liquid or the solution shape.Can spend its solvent, can be ion exchanged water, Purified Water, tap water, the water of ultrapure water etc. or organic solvent etc. are not though do special the qualification to it; But the instance as preferred organic solvent has methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol; Sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, 2-methyl-2-butanols, 2-methyl-2-amylalcohol, 3-methyl-3-amylalcohol; 2-methyl-2-hexanol, 3-ethyl-3-amylalcohol, the primary of the carbonatoms 1～10 of 2 etc., the second month in a season or tertiary alcohols; Or the glycols of terepthaloyl moietie or Diethylene Glycol etc.; Or the ethers of THF or dioxane etc.; Or Ethylene Glycol Methyl ether, glycol ethyl ether, the glycol ethers of diethylene glycol monomethyl ether or diethylene glycol monoethyl ether ether etc.; Acetonitrile, cyanobenzene, N, DMAC N,N, oil of mirbane, the aprotic, polar property solvent of N-Methyl pyrrolidone etc.; Or benzene or toluene, YLENE, phenylmethylether or the alkyl as chlorobenzene-, alkoxyl group-or the aliphatics or the aromatic hydrocarbons of halogen-substituted benzene etc.; Or pyridine, the heteroaromatic of picoline or quinoline etc.And, the TR of reacting its under the situation of liquid, also can formula (VI) or reactant nitrile (VII) or reactant Succinic Acid two fat be used as solvent.Above-mentioned solvent also can use as mixture.The reaction of above-mentioned Succinic Acid two fat and nitrile is preferably carried out in the alcohol as solvent, the particularly second month in a season or the tertiary alcohol.In the preferred tertiary alcohol, the trimethyl carbinol and tertiary amyl alcohol are arranged.Be also to can be the mixture of halogen substituted benzene of aromatic hydrocarbons or the chlorobenzene etc. of these preferred solvents and toluene or YLENE etc. as very interesting in this relation.

As stated, between the processing of supply with pressing and being rotated through fluidic is with face the pressure equilibrium of applied pressure and the processing that will specifically control the 1st fluid and the 2nd fluid collaborate with face 1, between 2, in the film fluid.The 1st fluid and the 2nd fluid are mixed in this film fluid, make above-mentioned 2 kinds of substance reactions.More specifically, can make the reaction of Succinic Acid two fat and nitrile.

In addition, also can mix highly basic, be expressed as R with the degree of the reaction between face not influence in processing ₁The nitrile of-CN or be expressed as R ₂The nitrile of-CN or the mixture of these nitriles, and whole fluid of Succinic Acid two fat make as the 1st fluid or the 2nd fluid and be used for implementing.

More specifically, can synthesize diketo pyrrolo-pyrrole pigment(DPP pigment), under this situation, can be at pigment dispersing agent, be preferably in the presence of the dispersion agent based on diketopyrrolopyrroles and quinacridine ketone, carry out the reaction of above-mentioned Succinic Acid two fat and nitrile.Such dispersion agent for example can be enumerated the compound of following formula.

[chemical formula 4]

In the above-mentioned formula, R30, R40 and R50 are independent inequality, can be hydrogen respectively, chlorine, bromine, fluorine, nitro, C1～C6 alkyl, C1～C6 alkoxyl group, benzamido-, homocyclic ring or heteroaromatic base, particularly, hydrogen or methyl; Q is quinacridine ketone group or diketopyrrolopyrrolecocrystals base, is preferably from can be by F Cl; Br, C1～C4-alkyl, C1～C4-alkoxyl group; In C1～substituted carboxylic acid amides of C6-alkyl and the phenoxy, 1,2 of selection; 3 or 4 substituted quinacridine ketone groups of substituting group, or as substituted diketopyrrolopyrrolecocrystals base as stated, m is 0.1～4.

In addition, as dispersion agent, can enumerate the compound of following formula.In the formula, R30, R40, R50, m, and Q are respectively like above-mentioned definition.

[chemical formula 5]

In addition, as dispersion agent, can enumerate the compound of following formula.In the formula, R30, R40, R50, m, and Q, like above-mentioned definition, R60 is R30 respectively, any one among R40 or the R50, preferred R30～R60 is respectively hydrogen, methyl or chlorine.

[chemical formula 6]

In addition, as dispersion agent, can enumerate the compound of following formula.

[chemical formula 7]

In the above-mentioned formula, Q such as above-mentioned definition; S and n are 0～4 independently, but two sides are not zero simultaneously; E ⁺Be H ⁺Or Li for example ¹⁺, Na ¹⁺, K ¹⁺, Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺, Mn ²⁺, Cu ²⁺, Ni ²⁺, Co ²⁺, Zn ²⁺, Fe ²⁺, Al ³⁺, Cr ³⁺Or Fe ³⁺Deng, the metallic cation M of 1～5 main family of the periodic table of chemical element or 1 or 2 or 4～8 transition group ^F+Suitable M ^F+/ f (f is 1,2 or 3); Ammonium ion N+R9R10R11R12; R9, R10, R11 and R12 are Wasserstoffatoms respectively independently; C1～C30-alkyl, C2～C30-thiazolinyl, C5～C30-naphthenic base; Phenyl; Benzyl) or (gathering) epoxy alkane of formula-[CH (R80)-CH (R80)-O] k-H (k is that 1～30,2 R80 are hydrogen, C1～C4-alkyl or their combination under the situation of k＞1 independently) (C1～C8)-alkyl-phenyl, (C1～C4)-alkylidene group-phenyl (example:; Alkyl, thiazolinyl, naphthenic base, phenyl, or also can be by amino, hydroxyl and/or carboxyl substituted as R9, R10, R11 and/or the R12 of alkyl phenyl; Or R9 and R10 and quaternary nitrogen atoms be integrally formed, for example, pyrrolidone, tetrahydroglyoxaline, hexamethylene imine, piperidines, the such ground of piperazine or morpholine type also can form according to hope and have the O of being selected from, S and N and then other heteroatomic 5～7 Yuans saturated ring system; Or R9, R10 and R11 and quaternary nitrogen atoms are integrally formed; For example pyrroles, imidazoles, pyridine, picoline, pyrazine; The such ground of quinoline or isoquinoline 99.9 type; Has the O of being selected from according to hope, S and N and then other heteroatoms and can be condensed into other ring, also can form 5～7 Yuans aromatic ring according to hope; Or E+ has the ammonium ion of following formula for regulation.

[chemical formula 8]

In the above-mentioned formula, R15, R16, R17 and R18 are (gathering) alkylidene group oxygen base of hydrogen or formula-[CH (R80)-CH (R80) O] k-H independently; K is that 1～30,2 R80 are hydrogen, C1～C4-alkyl independently or are their combination under the situation of k＞1; Q is 1～10, is preferably 1,2,3,4 or 5; P is 1～5, but p≤q+1; T is branching or nonbranched C2～C6-alkylidene group; Or under the situation of q＞1, T also can be the combination of branching or nonbranched C2～C6-alkylidene group; 2 Z bases are identical or inequality, and Z has the definition of Z1 or Z4; Z1 is for being expressed as-[X-Y] _qR ⁹¹Base.

-[X-Y] _qR ⁹¹Formula in, X is C2～C6-alkylidene group, C5～C7-ring alkylidene group or their combination; These bases also can be by C1～C4-alkyl of 1～4, hydroxyl, (other other the C5～C7-cycloalkyl substituted of C1～C4)-hydroxyalkyl and/or 1～2; Or under the situation of q＞1, X also can be the combination of above-mentioned meaning.

Y is-O-, or the base of following formula, or-the NR90 base; Or under the situation of q＞1, Y can be the combination of above-mentioned meaning; Q is 1～10, is preferably 1,2,3,4 or 5; R90 and R91 independently for Wasserstoffatoms, replacement do not replace or fluoridize or perfluorination branching or nonbranched (C1～C20)-alkyl, replacement or unsubstituted C5～C7-naphthenic base or replacement or do not replace or fluoridize or perfluorination (C2～C20)-thiazolinyl; These substituting groups can be hydroxyl, phenyl, and cyanic acid, chlorine, bromine, amino, C2～C4-acyl group or C1～C4-alkoxyl group is preferably 1～4; Or R90 and R91 and nitrogen-atoms be integrally formed, and forms saturated, unsaturated or aromatic 5～7 Yuans heterocycle; Those rings also can have the nitrogen of other other of 1 or 2, and oxygen or sulphur atom also can have by OH phenyl; CN, Cl, Br; Select among the crowd that C1～C4-alkyl, C1～C4-alkoxyl group, C2～C4-acyl group and formamyl form 1; 2 or 3 substituting groups replace, 1 or 2 benzo condensation saturated, unsaturation or aromatic carbocyclic ring or heterocycle; Z4 is a hydrogen, hydroxyl, and amino, phenyl, (C1～C4)-alkylidene group-phenyl, C5～C7-naphthenic base or C1～C20-alkyl; This benzyl ring, (C1～C4)-alkylidene group-phenyl and alkyl also can be by from Cl, Br; CN, NH2, OH, C6H5; Single-, two-or three-C1～C4-alkoxyl group replacement C6H5, formamyl, C2～C4-acyl group and C1～C4-alkoxyl group (example: more than 1 of crowd who methoxy or ethoxy) forms; For example 1,2,3 or 4 substituting groups replace; Above-mentioned benzyl ring and (C1～C4)-alkylidene group-phenyl also can be replaced by NR90R91 (R90 and R91 as above define); Or abovementioned alkyl is perfluorination or is fluoridized.

[chemical formula 9]

In addition, as dispersion agent, can enumerate the compound of following formula.

[Chemical formula 1 0]

In the above-mentioned formula, R15 is a hydrogen, chlorine, bromine, fluorine, C1～C6-alkyl, C1～C6-alkoxyl group, phenyl, two-(C1～C6-alkyl) amino, C1～C6-alkylthio, thiophenyl or phenoxy; Preferably R15 is at 4 and phenyl bonding; Q such as above-mentioned definition; The compound of formula (IX) has 0～6 SO3-E+ base; E such as above-mentioned definition.

In addition, as dispersion agent, can enumerate the compound of following formula.In the formula, R30, R40, m and Q are respectively like above-mentioned definition.

[Chemical formula 1 1]

Method of the present invention, further preferred use based on containing of quinacridine ketone and diketopyrrolopyrroles sugared pigment dispersing agent carry out.

Under the situation of the reaction of above-mentioned Succinic Acid two fat and nitrile, also can use and be selected from tensio-active agent, weighting agent, stdn agent; Resin, skimmer, dust-proofing agent, spreading agent; The shading tinting material, preservatives, dry delayed-action activator, rheology is regulated the auxiliary of their combination of additive.Negatively charged ion system, positively charged ion system and the material of nonionic system or their mixture etc. are arranged in useful tensio-active agent.At useful negatively charged ion is in the material, lipid acid taurate (tauride) class is for example arranged, lipid acid N methyl taurine salt, lipid acid hydroxyethylsulfonic acid class; Alkyl phenyl sulfonic acid class, alkyl naphthalene sulfonic acid class, alkyl phenol polyoxyethylene glycol ether sulfuric acid based; Fatty alcohol polyglycol ether sulfuric acid based, fatty amide polyglycol ether sulfuric acid based, salts of alkyl sulfosuccinates class; Alkenyl succinic acid monoesters class, poly alkyl alcohol glycol ester sulfo-succinic acid class, alkansulfonic acid class; The lipid acid glutamic acid-type, salts of alkyl sulfosuccinates acids, lipid acid sarcosinates; 16 carbonic acid for example, the fatty acid of Triple Pressed Stearic Acid and oleic acid etc.; Group aliphatic resin for example; The resinous acid of naphthenic and sylvic acid etc.; The alkali soluble resin of rosin sex change maleic acid resin etc., and based on cyanuric chloride, taurine, N, the soap that an alkali metal salt of the condensation product of N '-diethyl amino propylamine and Ursol D is such etc.As the special preferably an alkali metal salt of resinous acid is resin soap.At useful positively charged ion is in the material, and quaternary ammonium salt is for example arranged, fatty amine alkoxide class; Alkoxylate polyamines class, the amino polyoxyethylene glycol ethers of aliphatics, aliphatics amine; By aliphatics amine or aliphatics alcohols deutero-two-with the polyamines class; By these two-with polyamines deutero-alkoxide class, by the imidazolines of fatty acid derived, and these positively charged ions are the salt of material etc.At useful nonionic is in the material; The amine oxide class is for example arranged, fatty alcohol polyoxyethylene glycol ethers, fatty acid polyglycol ester class; The betaines of aliphatic amide N-CAB class etc.; The phosphonic acid ester of aliphatics alcohols or fatty alcohol polyoxyethylene glycol ethers, fatty amide ethoxylate class, fatty alcohol-alkylene oxide adducts and alkyl phenol polyoxyethylene glycol ether class etc.

Two sides of above-mentioned dispersion agent and auxiliary; Or; The arbitrarily only side of dispersion agent or auxiliary only is present in the first fluid and second fluidic and also can implements among either party, also can with above-mentioned first fluid, different, new the 3rd fluid of second fluid in implement.

The salt that also can the reaction with above-mentioned Succinic Acid two fat and nitrile be obtained in addition, is hydrolyzed.State on the implementation under the situation of hydrolysis, the fluid that comprises at least a formed material of reaction that contains above-mentioned nitrile and above-mentioned succinate and the fluid of hydrolytic reagent are collaborated between handling with face.Method as the interflow; Can implement as follows: the fluid of the formed material of reaction that will contain above-mentioned nitrile and above-mentioned succinate is once more as first fluid; As second fluid, the first fluid and second fluid are collaborated between handling with face the fluid that contains a kind of hydrolytic reagent at least.As the alternate manner of implementing, also can implement as follows: carry out the reaction of above-mentioned Succinic Acid two fat and nitrile in processing with the upper reaches between face, handling with the dirty reaction that contains the fluid and the hydrolytic reagent of the reactant that obtains between face.In addition, also can implement as follows: use handling the fluid that has mixed hydrolytic reagent in the fluid that is not containing Succinic Acid two fat or nitrile with the reaction between face with not bringing effect.

Employed hydrolytic reagent in the salt that the reaction with above-mentioned Succinic Acid two fat and nitrile obtains is not done special qualification, but preferably water, alcohols and acids, or alcohol or acids and their mixture, and suitable that selected and above-mentioned further different solvent.In useful alcohol, methyl alcohol is for example arranged, ethanol, Virahol, isopropylcarbinol, the trimethyl carbinol and tertiary amyl alcohol etc.Acid for example is hydrochloric acid, the mineral acid of phosphoric acid and preferably sulfuric acid etc.; Or formic acid, acetate, propionic acid, butyric acid, hexane acid, oxalic acid, TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M., phenylacetic acid, Phenylsulfonic acid or tosic acid, the aliphatics of preferred acetate and formic acid or acid mixture etc. or the carboxylic-acid or the sulfonic acid class of fragrance.

Claims (7)

1. the method for manufacture of a particulate; It is characterized in that; Through between 2 processing can keeping slight gap below the 1mm near counterrotating 2 processing discretely between with face, will keep with this slight gap are with face as the stream that is processed liquid; Formation is processed the pressure film of liquid, in this pressure film, carries out separating out of particulate.

2. the method for manufacture of a particulate; It is characterized in that; Can near 2 processing of relative displacement discretely with face between the multiple liquid that is processed of supply; Through the supply that comprises this liquid press and between the processing that is rotated is with face applied pressure to the power of direction of closing and balance to the pressure of the power of detaching direction, processing is maintained slight gap with the distance between face, 2 processing will keeping with this slight gap with between face as the described stream that is processed liquid; Form the pressure film that is processed liquid thus, in this pressure film, carry out separating out of particulate.

3. according to claim 1 or claim 2 the method for manufacture of particulate is characterized in that, comprise the liquid that is processed of multiple liquid, carries out the separating out of particulate with the state that has been stirred, has mixed in described 2 processing in the said pressure film between face.

4. like the method for manufacture of each the described particulate in the claim 1 to 3, it is characterized in that the volume average particle size in the size-grade distribution of the particulate that obtains is 1nm～200nm.

5. like the method for manufacture of each the described particulate in the claim 1 to 4; It is characterized in that; The liquid that is processed that contains particulate after separating out is after described 2 processing further are stirred in the said pressure film between face, from handling with being discharged between face.

6. the method for manufacture of particulate as claimed in claim 2 is characterized in that,

Use following forced ultra-thin film rotating treatment unit: possess and give the fluid of pressure and press imparting mechanism, the 1st to handle with portion and can handle with portion with respect to the 1st and relatively handle with at least 2 processing of portion with portion, rotary drive mechanism that said the 1st processing relatively is rotated with portion with portion and the 2nd processing near the isolating the 2nd to being processed liquid; Described each handle with in the portion each other the position of subtend be provided with the 1st and handle to handle and use face with at least 2 processing of face, the part that described respectively processing has been given the stream that being processed of said pressure is that liquid flows through, quilt is sealed with the face formation with face and the 2nd;

Described two handle with face between with being processed the liquid uniform mixing, separating out more than 2 kinds,

The said the 1st handle with portion and the 2nd handle with in the portion, at least the 2 processing possesses load face with portion, and at least a portion of this load face is made up of with face described the 2nd processing,

This load face receives described fluid and presses imparting mechanism to give the pressure that is processed liquid and produce and make the 2nd to handle the power that moves with the isolating direction of face from the 1st processing with face,

Through can near separate and relatively be rotated the 1st handle that feeding is described between handling with face with face and the 2nd is processed liquid more than 2 kinds; This is processed liquid and passes through two while the film fluid that forms the regulation thickness and handle with between face, carries out the separating out of particulate with the state that has been stirred, has mixed in described 2 processing in the said pressure film between face.

7. like the method for manufacture of each the described particulate in the claim 1 to 6, it is characterized in that any of described multiple liquid, the particle that the particulate that does not contain than does not obtain is also big.

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