CN101606089A - Particle having multilayer structure - Google Patents

Abstract

The invention provides transmittance or the particle having multilayer structure of reflection and the easy manufacture method of the specific wavelength that can optionally make wide region.Particle having multilayer structure of the present invention is characterised in that, have with central core (L0) serve as nuclear and with respect to nuclear the center with concentric shape stacked more than 2 layers the layer (Ln) structure, the refringence of adjacent layer is 0.01～1.5, and at least 1 layer in central core (L0) and the layer (Ln) is metal oxide layer (M).The manufacture method of particle having multilayer structure of the present invention is characterised in that, comprise at least 2 kinds, at least 2 kinds of from the manufacturing process (10) that utilizes pulsed laser irradiation, the manufacturing process (20) that utilizes gas shape metallic compound, the manufacturing process (30) that utilizes sol-gel process, dual micella layer and the manufacturing process (40) that utilizes sol-gel process, selecting repeatedly or at least a kind repeatedly; Perhaps, comprise manufacturing process (50) that utilizes the dual micella layer of use or the manufacturing process (60) that uses opposite charges.

Description

Particle having multilayer structure

Technical field

The present invention relates to particle having multilayer structure.

Background technology

In the past, as particle with sandwich construction, for example disclose the capillary difference that satisfies with respect to water surpass 0.1 (mN/m) relation 2 kinds of polymeric layers with the alternately laminated layer high molecule particulate that forms more than 4 layers of concentric shape (for example, with reference to patent documentation 1), multilayer structure polymer particle (for example, with reference to patent documentation 2) that forms by crosslinked methyl methacrylate layer, cross-linking elasticity alkyl acrylate layer and hard thermoplastic methyl methacrylate layer etc.

Patent documentation 1: TOHKEMY 2004-35785 communique

Patent documentation 2: TOHKEMY 2004-352837 communique

Summary of the invention

But for particle in the past, existence can't optionally make the problem of the transmittance or the reflection of specific wavelength in wide region.

Problem of the present invention is, the transmittance of the specific wavelength that can optionally make wide region or the particle having multilayer structure of reflection are provided.In addition, also provide the method for making this particle having multilayer structure easily.

The feature main points of particle having multilayer structure of the present invention are, have with central core (L0) serve as nuclear and with respect to nuclear the center with concentric shape stacked more than 2 layers the layer (Ln) structure, the refringence (25 ℃) of adjacent layer is 0.01～1.5, and at least 1 layer in central core (L0) and the layer (Ln) is metal oxide layer (M).

The feature main points of the manufacture method of particle having multilayer structure of the present invention are, comprise at least 2 kinds, at least 2 kinds of from manufacturing process (10), (20), (30) and (40) selection repeatedly or at least a kind repeatedly.

About manufacturing process (10), at the dispersion liquid that is dispersed with central core (L0) (D0) or be dispersed with in the dispersion liquid (Dn) of multilayered particles, place the block of resin or metal oxide, make it produce fine particle to this block irradiated with pulse laser, thereby the surface at central core (L0) or multilayered particles forms resin bed (R) or metal oxide layer (M), obtain the multilayered particles dispersion liquid, obtain particle having multilayer structure thus;

About manufacturing process (20), has the central core (L0) of reactive group (a) or multilayered particles and gasiform metallic compound that the surface has reactive group (a) react it by heating, surface at central core (L0) or multilayered particles forms metal compound layer, obtain the metal compound layer particle, remove unreacted gasiform metallic compound then, metal compound layer particle and water vapor are reacted, make metal compound layer become metal oxide layer (M), obtain multilayered particles thus, thereby obtain particle having multilayer structure;

About manufacturing process (30), comprise from following operation (31), operation (32), operation (33) and operation (34) select at least a and obtain particle having multilayer structure, promptly

Operation (31): in dispersion liquid (D0) or dispersion liquid (Dn), add metal alkoxide, form metal oxide layer by sol-gel process on the surface of central core (L0) or multilayered particles, obtain the multilayered particles dispersion liquid, described dispersion liquid (D0) is scattered in the alcohol of carbon number 1～4 or the non-protonic solvent (E31) central core (L0) that is made of the resin with active hydrogen and obtains, and the multilayered particles that described dispersion liquid (Dn) makes the surface be made of the resin bed with active hydrogen is scattered in the alcohol of carbon number 1～4 or the non-protonic solvent (E31) and obtains;

Operation (32): to contain can take place that the reactive surfactant (S1) of the cationic of copolymerization or anionic property and surface have the multilayered particles of metal oxide layer with the precursor (m) of resin or the dispersion liquid of the central core (L0) that constitutes by metal oxide in

Copolymerization and the ionic reactive surfactant (S2) opposite with reactive surfactant (S1) and the precursor (m) of resin can take place with the precursor (m) of resin in interpolation, then,

Make the precursor (m) of reactive surfactant (S1), reactive surfactant (S2) and resin that copolymerization take place, form resin bed, obtain the multilayered particles dispersion liquid, the multilayered particles of emanating then on the surface of multilayered particles or central core (L0);

Operation (33): to contain can take place that the reactive surfactant (S1) of the cationic of copolymerization or anionic property and surface have the multilayered particles of resin bed with the precursor (m) of resin or the dispersion liquid of the central core (L0) that constitutes by resin in,

Copolymerization and the ionic reactive surfactant (S2) opposite with reactive surfactant (S1) and the precursor (m) of resin can take place with the precursor (m) of resin in interpolation, then,

Make the precursor (m) of reactive surfactant (S1), reactive surfactant (S2) and resin that copolymerization take place, form resin bed, obtain the multilayered particles dispersion liquid, the multilayered particles of emanating then on the surface of multilayered particles or central core (L0);

Operation (34): in dispersion liquid (D0) or dispersion liquid (Dn), add metal alkoxide, form metal oxide layer by sol-gel process on the surface of central core (L0) or multilayered particles, obtain the multilayered particles dispersion liquid, described dispersion liquid (D0) is scattered in the alcohol of carbon number 1～4 or the non-protonic solvent (E31) central core (L0) that is made of the metal oxide with active hydrogen and obtains, and the multilayered particles that described dispersion liquid (Dn) makes the surface be made of the metal oxide layer with active hydrogen is scattered in the alcohol of carbon number 1～4 or the non-protonic solvent (E31) and obtains;

About manufacturing process (40), in dispersion liquid (D0) or dispersion liquid (Dn), add metal alkoxide, form metal oxide layer by sol-gel process on the surface of central core (L0) or multilayered particles, obtain the multilayered particles dispersion liquid, described dispersion liquid (D0) is scattered in the alcohol of carbon number 1～4 or the non-protonic solvent (E31) central core (L0) that is made of resin with active hydrogen or metal oxide and obtains, and the multilayered particles that described dispersion liquid (Dn) makes the surface be made of resin bed with active hydrogen or metal oxide layer is scattered in the alcohol of carbon number 1～4 or the non-protonic solvent (E31) and obtains.

The feature main points of the manufacture method of particle having multilayer structure of the present invention are, comprise manufacturing process (50) or manufacturing process (60), promptly

About manufacturing process (50), can take place in the dispersion liquid of the cationic of copolymerization or the reactive surfactant (S1) of anionic property and the central core (L0) that constitutes by resin or the surperficial multilayered particles that constitutes by resin bed with the precursor (m) of resin to containing

Copolymerization and the ionic reactive surfactant (S2) opposite with reactive surfactant (S1) and the precursor (m) of resin can take place with the precursor (m) of resin in interpolation, then,

Make the precursor (m) of reactive surfactant (S1), reactive surfactant (S2) and resin that copolymerization take place, form resin bed, obtain the multilayered particles dispersion liquid, then on the surface of central core (L0) or multilayered particles

The segregation multilayered particles carries out aforesaid operations repeatedly, obtains particle having multilayer structure;

About manufacturing process, (60), constitute and the surface has electric charge to being dispersed with by resin, (q) central core, (L0) dispersion liquid, (D0) or be dispersed with the surface and constitute and the surface has electric charge by resin bed, the dispersion liquid of multilayered particles (q), (Dn) in, the interpolation particle diameter is a central core, (L0) or the particle diameter of multilayered particles below 1/10th and have and electric charge, (q) opposite electric charge, (r) resin particle, (P0), thus at central core, (L0) or the surface of multilayered particles form and to comprise resin particle, (P0) resin bed, obtained the multilayered particles dispersion liquid, then

Carry out aforesaid operations repeatedly, obtain particle having multilayer structure.

Particle having multilayer structure of the present invention can optionally make the transmittance of specific wavelength or reflection { select the light of specific wavelength or make the function of the efficient scattering of light outstanding by interference of light in wide region.}。Therefore, even if the long-time use of particle having multilayer structure of the present invention also is difficult to fade, can be used as the colorant of high color purity etc.

In addition, if use manufacture method of the present invention, then can this particle having multilayer structure of easy manufacturing.

Description of drawings

Fig. 1 is for the treatment substrate that has used the sandwich construction spherical particle that obtains in embodiment 2 (CF-2), 4 (CF-4), 6 (CF-6), the curve map of the relation of expression transmission peak wavelength and transmissivity.

Fig. 2 is for the treatment substrate that has used the sandwich construction spherical particle that obtains in embodiment 8 (CF-8), 10 (CF-10), 12 (CF-12), the curve map of the relation of expression transmission peak wavelength and transmissivity.

Fig. 3 is for having used the relatively treatment substrate of the particle 1 (RF-1) of usefulness, 2 (RF-2), 3 (RF-3), the curve map of the relation of expression transmission peak wavelength and transmissivity.

Fig. 4 is for having used the relatively treatment substrate of the particle 4 (RF-4) of usefulness, 5 (RF-5), 6 (RF-6), the curve map of the relation of expression transmission peak wavelength and transmissivity.

Fig. 5 is for the treatment substrate after 1000 hours the ultraviolet ray of treatment substrate irradiation of having used the sandwich construction spherical particle that obtains in embodiment 2 (CF-2), 4 (CF-4), 6 (CF-6), represents the curve map of the relation of its transmission peak wavelength and transmissivity.

Fig. 6 is for the treatment substrate after 1000 hours the ultraviolet ray of treatment substrate irradiation of having used the sandwich construction spherical particle that obtains in embodiment 8 (CF-8), 10 (CF-10), 12 (CF-12), represents the curve map of the relation of its transmission peak wavelength and transmissivity.

Fig. 7 is for the treatment substrate after 1000 hours the ultraviolet ray of treatment substrate irradiation of having used the relatively particle 1 (RF-1) of usefulness, 2 (RF-2), 3 (RF-3), represents the curve map of the relation of its transmission peak wavelength and transmissivity.

Fig. 8 is for the treatment substrate after 1000 hours the ultraviolet ray of treatment substrate irradiation of having used the relatively particle 4 (RF-4) of usefulness, 5 (RF-5), 6 (RF-6), represents the curve map of the relation of its transmission peak wavelength and transmissivity.

Embodiment

＜particle having multilayer structure 〉

With regard to central core (L0), as long as it constitute nuclear, then without limits to its outer shape, but preferred average circularity is 0.96～1 spherical particle or average circularity is more than 0.7 and less than 0.96 non-spherical particle, further preferred average circularity is that 0.97～1 spherical particle and average circularity are 0.80～0.95 non-spherical particle, and preferred especially average circularity is that 0.98～1 spherical particle and average circularity are 0.85～0.93 non-spherical particle.

With regard to average circularity, calculate the circumferential distance (r1) that " maximum secting area " in the sectional area of particle is converted into positive bowlder, at least 1000 particles are obtained the value that this circumferential distance (r1) obtains divided by " the actual measurement circumferential distance (r2) " of maximum secting area, and average circularity is the arithmetic mean of these values.

About " maximum secting area ", make the dispersion liquid of sample flow into narrow gap and, the shadow that obtains be carried out Flame Image Process from perpendicular to the direction irradiates light that flows to, obtain therefrom.

About " actual measurement circumferential distance (r2) ", the Flame Image Process data that obtain when obtaining " maximum secting area " are segmented and are cut, and the cut-point on the counting circumference obtains therefrom.

All layers (Ln) are stacked with concentric shape with respect to the center of nuclear.In addition, layer (Ln) is more than 2 layers, and is preferred more than 3 layers, further preferred more than 4 layers, preferred especially more than 5 layers from the selective transmission of the light of the specific wavelength of wide region or the viewpoint of reflection etc., most preferably more than 6 layers.On the other hand, from the viewpoint made etc., preferred below 30 layers.

The n of layer (Ln) is the integer more than 1 corresponding to each layer, and the n of the layer adjacent with central core (L0) is 1, and n increases toward the outer side.That is, be laminated with layer (L1), be laminated with layer (L2) on the surface of layer (L1), be laminated with layer (L3), (L4) successively in the outside on the surface of central core (L0) ....

In all layers of central core (L0) and layer (Ln), the refringence (25 ℃) of adjacent layer is 0.01～1.5, and is preferred 0.05～1.5, further preferred 0.1～1.5, preferred especially 0.2～1.5, follow preferred 0.5～1.5, most preferably 1～1.5.If be this scope, it is better that the selective transmission of the light of the specific wavelength of wide region or reflection can become.If less than lower limit, be difficult to light is fully reflected or interferes, on the other hand,, then be difficult to obtain to be used to make the starting material of particle having multilayer structure if surpass higher limit.

About refractive index (25 ℃), go up the layer (Ln) that forms thickness v2 at the basement membrane (thickness v1) of refractive index with a1, obtain after the stacked film, measure the refractive index (W) of stacked film, obtain the refractive index (a2) of layer (Ln) according to following formula.

a2＝{W-(a1v1/(v1+v2))}×{(v1+v2)/v2}

Layer (Ln) thickness (μ m) separately is preferably 0.01～3.From the viewpoint of the selective transmission of the light of the specific wavelength of wide region etc., further preferred 0.01～0.2, preferred especially 0.02～0.1.On the other hand, from the viewpoint of the selective reflecting (diffusion) of the light of the specific wavelength of wide region etc., further preferred 0.1～3, preferred especially 0.5～2.

The thickness of central core (L0) (μ m) is preferably 0.05～3, and more preferably 0.1～2.5.

The thickness of central core (L0) is meant the mean distance from the central straight of the nuclear that forms central core (L0) to the central core surface.

Thickness about central core (L0) and layer (Ln), can be with the fixing particle having multilayer structure of resin, cut off by diamond cutter etc., use transmission electron microscope (TransmissionElectron Microscope:TEM) to measure the cross section of particle having multilayer structure.

About the standard deviation of at least 1 layer thickness in the layer (Ln), preferred below 30% from the viewpoint of the even interference of light, further preferred below 25%.

About the volume average particle size (μ m) of particle having multilayer structure of the present invention, from the viewpoint of excitation or scattering of light, preferred 0.1～20, further preferred 0.5～15, preferred especially 1～10.

About volume average particle size, the mensuration sample is scattered in the water, { for example the making corporate system LA-950} of institute in hole field measures the particle size distribution device of use light scattering mode.

About the volume (volume %) of central core (L0), from the viewpoint of optical transmission, based on the volume of particle having multilayer structure, preferred 5～98, further preferred 10～90.

About the volume of central core (L0), can be with the fixing particle having multilayer structure of resin, cut off by diamond cutter etc., use transmission electron microscope (Transmission ElectronMicroscope:TEM) to measure the cross section of particle having multilayer structure.

With regard to central core (L0) and layer (Ln), at least 1 layer in them is that metal oxide layer (M) gets final product, and all layers can be metal oxide layer (M), also can metal oxide layer (M) and other layer { for example resin bed (R) } mixing existence.

Mix under the situation about existing the structure that has preferably had other layer { for example resin bed (R) } and metal oxide layer (M) alternately laminated at other layer { for example resin bed (R) } and metal oxide layer (M).

Central core (L0) can be any one in metal oxide layer (M), other layer { for example resin bed (R) }, but preferable alloy oxide skin(coating) (M).

As the metal oxide that can constitute metal oxide layer (M), can enumerate monox, aluminium oxide, magnesium oxide, zinc paste, titanium dioxide, zirconia, antimony oxide and contain natural goods of these metal oxides etc.As natural goods, can enumerate talcum, kaolinton, smectite, mica, bentonitic clay, pyrophyllite clay and chrysotile etc.

Wherein, from the viewpoint of degree easy to manufacture and refractive index, preferably from monox, aluminium oxide, magnesium oxide, zinc paste and titanium dioxide, select at least a kind, at least a kind of further preferably from monox, aluminium oxide and titanium dioxide, selecting.

As other layer, comprise resin bed (R) and metal nitride layer etc.Wherein, from the viewpoint of degree easy to manufacture, preferred resin layer (R).

As the resin that can constitute resin bed (R), comprise non-coloring and have the resin of making film, viewpoint from the transparency and refractive index, preferably from polyurethane, polyester, vinylite, fluororesin and polyamide, select at least a kind, at least a kind of further preferably from vinylite, fluororesin and polyamide, selecting.

Preferably in resin bed (R), contain cross-linked resin.

As cross-linked resin, can enumerate and make the monomer that has 2 above vinyl in 1 molecule carry out the cross-linked vinyl resin that copolymerization forms, make the monomer or the prepolymer that have 3 above isocyanate group in 1 molecule carry out the crosslinking polyurethane resin that copolymerization forms, make the glycidyl that in 1 molecule, has more than 3, the monomer of amino or carboxyl or prepolymer carry out the cross-linked epoxy resin that copolymerization forms, make the amino that in 1 molecule, has more than 3, the monomer of carboxyl or anhydride group { 1,3-oxo-2-oxa-propylidene } or prepolymer carry out crosslinked polyamide that copolymerization forms etc.

Containing under the situation of cross-linked resin, the content (weight %) about cross-linked resin based on the weight of resin bed (R), is preferably 30～100, and further preferred 50～100.

Particle having multilayer structure of the present invention, to its outer shape without limits, preferred average circularity is that 0.96～1 spherical particle or average circularity are more than 0.7 and less than 0.96 non-spherical particle, further preferred average circularity is that 0.97～1 spherical particle and average circularity are 0.80～0.95 non-spherical particle, and preferred especially average circularity is that 0.98～1 spherical particle and average circularity are 0.85～0.93 non-spherical particle.The outer shape of particle having multilayer structure of the present invention is to a great extent by about the outer shape of central core (L0) institute.

At bed thickness is in the sandwich construction of 0.01～0.2 μ m, certain layer take place the light of reflection and within it the layer in the layer of side or the outside light that takes place to reflect interfere mutually, so the wavelength light corresponding with bed thickness and refractive index presents color (presenting schemochrome).In addition, schemochrome is because of the visible various color of viewing angle, but is under the situation of spherical particle at particle having multilayer structure, and viewing angle becomes necessarily, visible a kind of color (monochromatic light).In addition, the refringence of adjacent layer is big more, and in addition, the number of plies is many more, and then reflection efficiency big more { reflected light increases with respect to the amount of incident light } obtains strong schemochrome.

On the other hand, be in the sandwich construction of 0.1～3 μ m at bed thickness, interference of light can not take place, but reflect at each layer.In addition, the number of plies is many more, more light scattering efficiently can take place.In addition, compare with spherical particle, the light diffusion more can take place in non-spherical particle efficiently.

Preferably contain colorant (D) at least 1 layer in central core (L0) and layer (Ln).As colorant (D), from the purity of color development light and the viewpoint of color reproduction, at least a kind of preferably from dyestuff, pigment and fluorophor, selecting.

As dyestuff, can enumerate the purple N of acid alizarine, acid black, acid blue, acid chrome violet K, acid fuchsin, acid green, acid orange, acid red, acid violet 6B, directly yellow, direct orange (directly Orenge), direct purple, the direct derivant of green, the food yellow 3 of indigo plant, direct green, media Huang, media orange, media purple, media and these dyestuffs.In addition, also can use these dyestuffs { acid dyes of azo system, xanthene system or phthalocyanine system } in addition, also can use C.I. solvent blue 44,38, C.I. solvent orange 45 (C.I.Solvent Orenge 45), rhodamine B, rhodamine 110,2, the derivant of 7-naphthalenedisulfonic acid and these dyestuffs.

As pigment, can enumerate red stain { potpourri of C.I. paratonere 254 and C.I. paratonere 177 etc. }, green colourant { potpourri of C.I. pigment green 36 and C.I. pigment yellow 150 or C.I. pigment yellow 13 8 etc. } and blue colorant { C.I. pigment blue 15, C.I. alizarol saphirol 22, C.I. pigment blue 60 and C.I. alizarol saphirol 64 etc. } etc.

As fluorophor, be selected from inorganic phosphor { oxide of rare earth element (zinc, cadmium, magnesium, silicon and yttrium etc.) etc., sulfide, silicate, vanadate etc. } and organic fluorescent { fluorescein, eosin and oils (mineral oil) etc. } etc.Activator is selected from silver, copper, manganese, chromium, europium, zinc, aluminium, lead, phosphorus, arsenic and gold etc.Solvent is selected from sodium chloride, potassium chloride, magnesium carbonate and barium chloride etc.

Under the situation that contains colorant (D), the content (weight %) about colorant (D) based on the weight of particle having multilayer structure, is preferably 0.1～10, and further preferred 0.5～5.

The manufacture method of＜particle having multilayer structure 〉

At central core (L0) is under the situation of spherical resin layer, and central core (L0) is by acquisitions such as general emulsion polymerization, suspension polymerization, miniemulsion method or dispersion copolymerization methods.In addition, be under the situation of spherical metal oxide layer (M), at central core (L0) by acquisitions such as sol-gel processes.

At central core (L0) is under the situation of non-spherical resin layer, and central core (L0) waits and makes by following known method { methods of (1)～(5) }.

(1) in emulsion polymerization and suspension polymerization etc., in external phase, add tackifier { high molecular weight water soluble polymer (polyvinyl alcohol, carboxymethyl cellulose and polyvinyl pyrrolidone etc.) }, under agitation make the method for its polymerization reaction take place.

(2) thermoplastic resin is scattered in the solvent, is heated to more than the glass transition temperature of thermoplastic resin, the method that under high shear stirs, cools off and make.

(3) make the resin particle swelling with solvent, under high shear solvent is removed and the method made.

(4) in emulsion polymerization and suspension polymerization etc., make monomer copolymerization take place, utilize the volumetric contraction that causes by cross-linking reaction with crosslinking chemical, and the method for making.

(5) ground resin particles or metal oxide particle and the method made.

Wherein, from the viewpoint of light scattering and surface smoothing, the method for preferred (1), (2) or (3).

At central core (L0) is under the situation of non-spherical metal level, and central core (L0) can wait by the method for using the method for above-mentioned (1) in comminuting method and sol-gel process and make.

Particle having multilayer structure of the present invention, can by with central core (L0) serve as nuclear and with respect to nuclear the center with concentric shape stacked more than 2 layers the layer (Ln) make.

As making with central core (L0) is nuclear and the method for making particle having multilayer structure with respect to the center of nuclear with the stacked layer (Ln) more than 2 layers of concentric shape, comprise manufacture method (1), manufacture method (2) and other manufacture method (3), described manufacture method (1) comprise at least 2 kinds, at least 2 kinds of from manufacturing process (10), (20), (30) and (40) selection repeatedly or a kind repeatedly; Described manufacture method (2) comprises manufacturing process (50) or manufacturing process (60).

1. manufacture method (1)

1-1. manufacturing process (10)

Manufacturing process (10) comprising: in the dispersion liquid that is dispersed with central core (L0) (D0), place the resin of cambium layer (L1) or the block of metal oxide, to this block irradiated with pulse laser, make it produce fine particle, surface at central core (L0) forms resin bed (R1) or metal oxide layer (M1), obtain 2 layers of particle dispersion { 2 layers of particle of preferably emanating then.}。

Then, can make up manufacturing process (20), (30) and/or (40) and obtain particle having multilayer structure.On the other hand, can { preferably be dispersed with 2 layers of dispersion of nano-particles liquid of having emanated } to 2 layers of structured particles dispersion liquid and (D1) implement operation same as described above, and obtain 3 layers of particle.And then by carrying out this operation repeatedly, thereby can obtain particle having multilayer structure.In addition, can also prepare the dispersion liquid (Dn) that is dispersed with the multilayered particles that obtains in manufacturing process (20), (30) and/or (40), similarly carry out with above-mentioned, thereby obtain particle having multilayer structure.

Preferred center layer (L0) or multilayered particles are to the even dispersion that is separated into of solvent (E1).

As process for dispersing, be not particularly limited method of preferably use the method for known homogenizer, disperseing by ultrasound wave etc.

As solvent (E1), so long as do not absorb the solvent of pulse laser, just be not particularly limited, for example can make water and common commercially available organic solvent { acetone, methyl ethyl ketone, methyl alcohol, ethanol, toluene, dimethylbenzene, hexane, diox, THF, DMF and DMSO etc. }.

About the content (weight %) of central core (L0) or multilayered particles, based on the weight of dispersion liquid (D0) or dispersion liquid (Dn), preferred 0.001～10, further preferred 0.005～5.

The block of resin or metal oxide preferably is placed on the bottom surface or the side of the container that dispersion liquid (D0) or dispersion liquid (Dn) are housed.

The wavelength of pulse laser (nm) is preferred 200～700, and is further preferred not by the wavelength of solvent absorbing.

The output of pulse laser (mJ/pulse) preferred 30～100.

Device as making pulsed laser action is not particularly limited, preferred YAG laser oscillation apparatus.

When irradiated with pulse laser, the temperature of dispersion liquid (D0) or dispersion liquid (Dn) (℃) be preferably 5～80.

The volume of dispersion liquid (D0) or dispersion liquid (Dn) for 1 pulsed laser action device, is preferably 10～100ml.

About the use amount (volume %) of the block of resin or metal oxide, the volume based on dispersion liquid (D0) or dispersion liquid (Dn) is preferably 1～10.

Block by illuminated pulse laser produces fine particle, and this fine particle forms resin bed (R) or metal oxide layer (M) attached to the surface of central core (L0) or multilayered particles.

Be formed with the multilayered particles of resin bed (R) or metal oxide layer (M), emanated by centrifuging, filtration under diminished pressure, pressure filtration or freeze drying etc.

1-2. manufacturing process (20)

Manufacturing process (20) comprising: the central core (L0) and the gasiform metallic compound that have reactive group (a) by heating react it, surface at central core (L0) forms metal compound layer, obtain after the metal compound layer particle, remove unreacted gasiform metallic compound, metal compound layer particle and water vapor are reacted, make metal compound layer become metal oxide layer (M), obtain 2 layers of particle.

Then, can make up manufacturing process (10), (30) and/or (40) and obtain particle having multilayer structure.On the other hand, 2 layers of particle and gasiform metallic compound are reacted, carry out operation same as described above, and obtain 3 layers of particle.And then carry out this operation repeatedly, thereby can obtain particle having multilayer structure.In addition, the multilayered particles and the gas shape metallic compound that obtain in manufacturing process (10), (30) and/or (40) are reacted, similarly carry out with above-mentioned, thereby obtain particle having multilayer structure.Need to prove that carrying out repeatedly under the situation of aforesaid operations, gasiform metallic compound can use the kind identical with initial kind, can also use variety classes.

As reactive group (a), so long as the group that can react with gasiform metallic compound just without limits, preferably has the group of active hydrogen, further preferred hydroxyl, carboxyl and amino.

As gasiform metallic compound, so long as and the compound that reacts of reactive group (a), just be not particularly limited, but preferred halogenated titanium { titanium chloride etc. }, aluminum alkyls { trimethyl aluminium etc. } and silicon halide { silicon chloride etc. }.

As reaction vessel, preferred heat-resistant pressure vessel further preferably is provided with the container that heating arrangement, gas introduction port and reliever and material can not react with gasiform metallic compound.

About the moisture in the reaction vessel, from the viewpoint of the stability of metallic compound, preferred moisture is few, more preferably below the 100ppm, is preferably below the 10ppm especially.

As temperature of reaction (℃), preferred 30～500.

For remove the unreacted metal compound, can use the method that will reduce pressure in the container, and to carrying out inert gas (nitrogen and helium etc.) method of replacement etc. in the container.

The temperature of reaction of metal compound layer and water vapor (℃) be preferably 30～500.

The each layer that forms about 0.2nm of manufacturing process (20) carries out manufacturing process (20) repeatedly by using metallic compound of the same race, can form target thickness.

Therefore, when using manufacturing process (20), preferably repeatedly repeat identical manufacturing process (20) until the thickness that reaches regulation.

1-3. manufacturing process (30)

Manufacturing process (30) comprises at least a kind that selects from operation (31), operation (32), operation (33) and operation (34).

That is, the manufacture method that comprises manufacturing process (30) comprises: from operation (31), operation (32), operation (33) and operation (34), select at least 2 kinds, at least 2 kinds repeatedly or at least a kind repeatedly; The perhaps combination of they and manufacturing process (10), (20) and/or (40).Need to prove, under the situation of carrying out operation (32) and/or operation (33) repeatedly, owing to be used alternatingly reactive surfactant with counter ion, so be necessary after obtaining the multilayered particles particle dispersion, multilayered particles is emanated { centrifuging, filtration under diminished pressure, pressure filtration and freeze drying etc. }, carry out next process then.On the other hand, under the situation of carrying out operation (31) and/or operation (34) repeatedly, after obtaining the multilayered particles particle dispersion, and unnecessary segregation multilayered particles, but preferably afterwards, carry out next process in emanate { centrifuging, filtration under diminished pressure, pressure filtration and freeze drying etc. }.

1-3-1. operation (31)

As active hydrogen, be included in hydrogen atom contained in hydroxyl, carboxyl, amino or the sulfydryl.

As the alcohol of carbon number 1～4, comprise methyl alcohol, ethanol, isopropyl alcohol, propyl alcohol and butanols.Wherein, preferred alcohol, ethanol and isopropyl alcohol.

As non-protonic solvent, comprise ketone { acetone and methyl ethyl ketone etc. }, ester { ethyl acetate and butyl acetate etc. }.Wherein, preferable methyl ethyl ketone, ethyl acetate and butyl acetate.

About the concentration (volume %) of central core (L0) or multilayered particles, based on the volume of dispersion liquid (D0) or dispersion liquid (Dn), preferred 0.01～10, further preferred 0.02～8.If be this scope, it is better that the standard deviation of bed thickness becomes.

Central core (L0) or multilayered particles are preferably even dispersion to the dispersion of alcohol or non-protonic solvent (E31).

As process for dispersing, be not particularly limited method of preferably use the method for known homogenizer, disperseing by ultrasound wave etc.

As metal alkoxide, comprise alkali metal lithium, sodium and potassium etc. }, the alkoxide { carbon number 1～4 of earth alkali metal { magnesium and calcium etc. }, heavy metal { titanium, zirconium, iron, copper etc. }, aluminium or silicon; Methoxide, ethylate, propylate, isopropoxide or normal butyl alcohol salt etc. } etc.Wherein, the alkoxide of preferred heavy metal, aluminium or silicon.

Sol-gel process can application of known method { for example, after in dispersion liquid (D0) or dispersion liquid (Dn), having added small amount of hydrochloric acid, add the method that metal alkoxide makes its reaction }.

As temperature of reaction (℃), preferred 5～150, further preferred 10～80.

Preferably in reaction, use catalyzer.

As catalyzer, can enumerate metallic catalyst { tin catalyst (dibutyl tin laurate, stannous octoate, stannous chloride and tetrabutyl zirconate etc.), plumbous catalyzer (plumbi oleas, lead naphthenate and octene lead plumbate etc.) etc. }, amine catalyst { triethylenediamine and dimethylethanolamine etc. }, acid catalyst { boron trifluoride, hydrochloric acid, p-toluenesulfonic acid and dodecylbenzene sulfonic acid etc. }, base catalyst { amine and alkaline earth metal hydroxide etc. } and salt { quaternary ammonium salt etc. } etc.

In the metal oxide layer that forms by operation (31), there is active hydrogen to exist.Therefore, can be in operation (31) application procedures (31) or operation (34) afterwards.

1-3-2. operation (32)

Reactive surfactant (S1) so long as have cationic or the anionic surfactant that the group of copolymerization can take place with the precursor (m) of resin, just is not particularly limited.

As can with the group of precursor (m) copolymerization, can enumerate vinyl, isocyanate group, blocked isocyanate base, glycidyl, amino, hydroxyl and carboxyl etc.

Reactive surfactant as anionic property, preferably { for example, ELEMINOL JS-2: Sanyo changes into industrial group's system, and (" ELEMINOL " is the registered trademark of the said firm to the sodium salt of the alkyl of illustration sulfosuccinic acid (carbon number 12～13) allyl diester.), the sulphonic acid ester sodium salt { for example, ELEMINOL RS-30: Sanyo changes into industrial group's system } of polyoxyalkylene methacrylate, and the sulfuric ester ammonium salt of allyl yloxymethyl polyoxyethylene hydroxy alkyl ether { Aqualon KH-10: (" Aqualon " is the registered trademark of the said firm to the first industrial drugmaker system.) etc.

As the reactive surfactant of cationic, but preference is shown in the compound that has methacryloxy and trialkyl ammonium in a part { methacryloxyethyl amino carbonyl oxy-ethyl-trimethyl ammonium methyl sulphate }, reaches methacrylic acid trimethyl ammonium diethylaluminum monochloride salt (document; The 13rd polymer microsphere body discussion 2B10 Seiko Epson) etc.

About the use amount (weight %) of reactive surfactant (S1), preferred 1～100 based on the weight of the precursor (m) of resin, further preferred 1.5～80.If be this scope, it is better that the standard deviation of bed thickness can become.

Preferably have electric charge (q) on the surface of multilayered particles or central core (L0), further preferably have above ζ (zeta) current potential of 0.1mV or-following ζ (zeta) current potential of 0.1mV.

In addition, this electric charge (q) and reactive surfactant (S1) is ionic preferred opposite.For example, be that reactive surfactant is preferably cationic under the situation about bearing at electric charge (q).On the other hand, for example under electric charge (q) was positive situation, reactive surfactant was preferably anionic property.

As multilayered particles with electric charge (q) or central core (L0), preferred surface has ionic group.As ionic group, can enumerate anionic group { carboxylic acid ester groups (CO ₂ ^-), phosphonate group (PO (O ^-) ₂Or-PO (OH) (O ^-)) and sulfonic group (SO ₃ ^-) base etc., and cation group { ammonium (NH ₃ ⁺), quaternary ammonium group (NR ₃ ⁺R is the alkyl of carbon number 1～3), sulfonium base (SH ₂ ⁺) Ji Phosphonium base (PH ₃ ⁺) etc.

About containing the dispersion liquid of reactive surfactant (S1) and multilayered particles or central core (L0),, make water, the alcohol of carbon number below 4 etc. as dispersion solvent.

Central core (L0) or multilayered particles are preferably even dispersion to the dispersion of dispersion solvent.

As process for dispersing, be not particularly limited method of preferably use the method for known homogenizer, disperseing by ultrasound wave etc.

About the content (volume %) of central core in the dispersion liquid (L0) or multilayered particles, based on the volume of dispersion liquid, preferred 0.01～50.

Reactive surfactant (S2) so long as have group and ionic and reactive surfactant (S1) the opposite surfaces activating agent that copolymerization can take place with the precursor (m) of resin, just is not particularly limited.

If reactive surfactant (S1) is an anionic property, then reactive surfactant (S2) is a cationic, and on the other hand, if reactive surfactant (S1) is a cationic, then reactive surfactant (S2) is an anionic property.

As can with the group of precursor (m) copolymerization, can enumerate vinyl, isocyanate group, blocked isocyanate base, glycidyl, amino, hydroxyl and carboxyl etc.

As reactive surfactant (S2), comprise and the identical surfactant of reactive surfactant (S1).

The operating weight of reactive surfactant (S1) and reactive surfactant (S2) is preferably 1/2～2/1 than { (S1)/(S2) }.

Precursor (m) as resin becomes the material of resin so long as react, and just can be any precursor, comprises vinyl monomer, contains the compound of glycidyl etc.

About the use amount (volume %) of the precursor (m) of resin because and the thickness of resin bed direct relation is arranged, so based on the volume of multilayered particles or the volume of central core (L0), preferred 0.1～100.If be this scope, then the standard deviation of bed thickness can become better.

The method of copolymerization takes place as the precursor (m) that makes reactive surfactant (S1), reactive surfactant (S2) and resin, can use known method, but the preferred method that adopts heat, ultraviolet ray irradiation (UV) or electron beam irradiation (EB), further preferred method by heat.

Under the situation that adopts heat, as temperature of reaction (℃), preferred 30～160.

About operation (32), be to form 2 heavy micella layers on the surface of multilayered particles or central core (L0), enclose precursor (m) therein, make reactive surfactant (S1), reactive surfactant (S2) and precursor (m) that copolymerization take place, form the operation of resin bed thus.

1-3-3. operation (33)

Operation (33) is except being altered to " central core (L0) that the surface has the multilayered particles of metal oxide layer or is made of metal oxide " " central core (L0) that the surface has the multilayered particles of resin bed or is made of resin ", and all the other are identical with operation (32).

1-3-4. operation (34)

Operation (34) is except will " central core (L0) that is made of the resin with active hydrogen " or " multilayered particles that the surface is made of the resin bed with active hydrogen ", be altered to outside " central core (L0) that is made of the metal oxide with active hydrogen " or " multilayered particles that the surface is made of the metal oxide layer with active hydrogen ", all the other are identical with operation (31).

1-4. manufacturing process (40)

Operation (40) is in operation (31) or the preferred afterwards operation that obtains particle having multilayer structure by the segregation multilayered particles of operation (34).

Then, can make up manufacturing process (10), (20) and/or (30) and obtain particle having multilayer structure.In addition, can use the multilayered particles that obtains in manufacturing process (10), (20) and/or (30), similarly carry out with above-mentioned, thereby obtain particle having multilayer structure.Need to prove that carrying out repeatedly under the situation of aforesaid operations, metal alkoxide can use the kind identical with initial kind, also can use variety classes.

2. manufacture method (2)

2-1. manufacturing process (50)

Manufacturing process (50) emanates to multilayered particles afterwards and then carries out operation (33) repeatedly and obtain the operation of particle having multilayer structure in operation (33).

2-2. manufacturing process (60)

As being made of resin and the surface has the central core (L0) of electric charge (q), it is { identical with the ionic group in the operation (32) that preferred surface has an ionic group.}。

As electric charge (q), ζ (zeta) current potential that preferred 0.1mV is above or-following ζ (zeta) current potential of 0.1mV.

As the dispersion solvent of dispersion liquid, make water, the alcohol of carbon number below 4 etc.

Central core (L0) or multilayered particles are preferably even dispersion to the dispersion of dispersion solvent.

As process for dispersing, be not particularly limited method of preferably use the method for known homogenizer, disperseing by ultrasound wave etc.

About the content (volume %) of central core in the dispersion liquid (L0) or multilayered particles, based on the volume of dispersion liquid, preferred 0.01～50, further preferred 0.02～40.

As resin particle (P0), if having the electric charge (r) opposite and particle diameter with electric charge (q) be central core (L0) or multilayered particles particle diameter 1/10th, just be not particularly limited.

Resin particle (P0) obtains by general emulsion polymerization, suspension polymerization, miniemulsion method or dispersin polymerization etc.Wherein, from the viewpoint of particle diameter control, preferred emulsion polymerization.

The volume average particle size of central core (L0) or multilayered particles (μ m) is preferably 0.1～20.

The volume average particle size of resin particle (P0) (μ m) preferred 0.01～2, further preferred 0.02～1.

About the content (volume %) of central core (L0) or multilayered particles, based on the volume of dispersion liquid, preferred 0.01～50.

About the content (weight %) of resin particle (P0), based on the weight of central core (L0) or multilayered particles, preferred 0.1～100, further preferred 5～100.

When adding resin particle (P0) in dispersion liquid (Dn), the temperature of dispersion liquid (Dn) and resin particle (P0) is preferably 5～40 ℃.

Be formed with the multilayered particles of resin bed, preferably emanate, use this dispersion liquid (the preferably multilayered particles of having emanated) to carry out identical operations repeatedly, make particle having multilayer structure by centrifuging, filtration under diminished pressure, pressure filtration or freeze drying etc.

3. other manufacture method (3)

Particle having multilayer structure of the present invention, if can with central core (L0) serve as nuclear and with respect to nuclear the center with concentric shape stacked more than 2 layers the layer (Ln), then except above-mentioned manufacture method, also can make by following known method.

3-1. manufacturing process (70)

The different block polymer of solubility parameter is dissolved in the organic solvent, uses surfactant in water, to disperse this solution, carry out desolventizing, obtain the manufacture method of particle having multilayer structure thus.

3-2. manufacturing process (80)

Utilize coupling agent etc. on the reactive group on the surface of central core (L0) or multilayered particles, to import vinyl, make vinyl monomer generation graft reaction, carry out this operation repeatedly, obtain the manufacture method of particle having multilayer structure thus.

3-3. manufacturing process (90)

By under dry type, making macroparticle and small-particle high velocity impact, form the layer of small-particle on the macroparticle surface, carry out this operation repeatedly, obtain the manufacture method of particle having multilayer structure thus.

3-4. manufacturing process (100)

In solvent, disperse macroparticle and small-particle, this solution of high-speed stirred, and, carry out this operation repeatedly at the surperficial layer that forms small-particle of macroparticle, obtain the manufacture method of particle having multilayer structure thus.

In these manufacture methods, preferably contain manufacturing process (10)～(60).

Need to prove, can make up manufacturing process (10)～(100).

As the example of combination, can enumerate operation (10) and (30), operation (20) and (30), operation (30) and (50), operation (30) and (60), reach operation (20) and (50) etc.Wherein, from the controlled viewpoint of refringence, preferable process (10) and (30), operation (20) and (30).

Particle having multilayer structure of the present invention can be used to show color filter, resin molding, coating material { pigmented finiss, antiglossing pigment, baffle reflection film with coating etc. } and optical diffusion film etc.In addition, can also be used as pigment, dyestuff.

About particle having multilayer structure of the present invention, being under the spherical situation, be suitable for showing color filter, under the spherical situation of right and wrong, be suitable for optical diffusion film.Being under any one the situation in spherical particle and the non-spherical particle, all be suitable for resin molding, coating material.

Can make by the following method about color filter, that is, { dispersion liquid of 5～20 weight %} and bonding agent etc. is sprayed onto on the glass substrate and with after its configuration, carries out drying for example to utilize inkjet nozzle will be dispersed with spherical particle having multilayer structure.

Optical diffusion film and resin molding can be made by the following method, promptly (1) carries out film the method for melting mixing, extruding and drawing and forming with resin and particle having multilayer structure, (2) particle having multilayer structure is scattered in the resin solution and it is carried out curtain coating and makes the method for film, and (3) carry out the method for polymerization etc. after being scattered in particle having multilayer structure in the monomer.

About the content (weight %) of particle having multilayer structure, based on the general assembly (TW) of film with resin and particle having multilayer structure, preferred 1～80, further preferred 5～50.

As the film resin, can enumerate optical resin { for example polymethylmethacrylate (PMMA), polycarbonate and polyester } and adhesive resin { for example urethane resin, epoxy resin, acryl resin and polyester } etc.

Coating material obtains by being blended in the starting material { bonding agent and solvent etc. } and the particle having multilayer structure of the present invention that use in known coating, the printing ink { being necessary to note that the shear stress that particle having multilayer structure can not caused by mixing destroys.}。

Embodiment

Utilize embodiment to further specify the present invention, the present invention is not limited to this.

Below, part expression weight portion, % represents weight %.

＜Production Example 1 〉: the manufacturing of the reactive surfactant of cationic

Make 2-(methacryloxy) ethyl isocyanate { trade name: Karenz MOI: clear and electrician's corporate system; " Karenz " is the registered trademark of the said firm.1 part of 100 part, 57 parts of dimethylaminoethanols, dibutyl tin laurate are after 80 ℃ of reactions 8 hours, in this solution and then add 81 parts of dimethyl suflfates, and then, obtain the reactive surfactant (S-1) { methylacryoyloxyethyl amino carbonyl oxy-ethyl-trimethyl ammonium methyl sulphate } of cationic 60 ℃ of reactions 4 hours.

＜Production Example 2 〉: the manufacturing of titanium dioxide spherical particle (central core)

After 7 parts of 200 parts of titanium tetraisopropylates, 750 parts of methyl ethyl ketones, polyvinyl pyrrolidone (number-average molecular weight 40000) are evenly mixed, be heated to 50 ℃, with 2 parts of 1 hour dropping 1% ammonia spirits.After the dropping, be heated to 80 ℃, reacted 8 hours, obtain containing the dispersion liquid of spherical Titanium particles (LB-1).With regard to spherical Titanium particles (LB-1), this dispersion liquid is carried out carrying out drying { 50 ℃ * 48 hours, dryer with the wind after centrifuging, the washing; Below identical., obtain { volume average particle size 2.7 μ m, average circularity 0.98} thus.

＜Production Example 3 〉

800 parts of ion exchange waters and neopelex are evenly mixed for 5 parts, obtained water.On the other hand, { ELEMINOL JS-2: Sanyo changes into industrial group's system: " ELEMINOL " is the registered trademark of the said firm with the reactive surfactant of 100 parts of styrene, 60 parts of divinylbenzenes, 20 parts of hydroxyethyl methylacrylates, 5 parts of azo dibutyronitriles, anionic property.15 parts evenly mix, obtain oil reservoir.Then, add oil reservoir to the aqueous phase full dose, use rotor-stator type dispersion machine [TK homogenizer: special machine chemical industry corporate system], after 4000rpm stirring 1 minute, move to pressure vessel with stirring apparatus, 85 ℃ of reactions 12 hours, { surface had active hydrogen (hydroxyl) to obtain containing spherical resin particle (LB-2).Dispersion liquid.With regard to spherical resin particle (LB-2), this dispersion liquid is carried out carrying out drying after centrifuging, the washing, obtain { volume average particle size 5.3 μ m, average circularity 0.98} thus.

＜Production Example 4 〉

After 50 parts of 750 parts of methyl ethyl ketones, 7 parts of polyvinyl pyrrolidones (number-average molecular weight 40000), spherical resin particle (LB-2) are evenly mixed, be heated to 50 ℃, with 2 parts of 1 hour dropping 1% ammonia spirits.Then,, be heated to 80 ℃, reacted 8 hours, obtain containing the dispersion liquid of 2 layers of structure spherical particle (LB-3) with dripping in 1 hour after 0.47 part of the tetraethoxysilane.With regard to 2 layers of structure spherical particle (LB-3), carry out carrying out drying after centrifuging, the washing, obtain { central core (L0): crosslinked polystyrene, silicon oxide layer (L1), volume average particle size 5.3 μ m, average circularity 0.98} thus.

＜Production Example 5 〉

Tetraethoxysilane is altered to " 0.55 part " from " 0.47 part ", in addition, similarly carries out, obtain 2 layers of structure spherical particle (LB-6) { volume average particle size 5.3 μ m, average circularity 0.98} with Production Example 4.

＜Production Example 6 〉

Tetraethoxysilane is altered to " 0.68 part " from " 0.47 part ", in addition, similarly carries out, obtain 2 layers of structure spherical particle (LB-9) { volume average particle size 5.4 μ m, average circularity 0.98} with Production Example 4.

＜Production Example 7 〉

Potpourri to 950 parts of ion exchange waters, 45 parts of spherical Titanium particles (LB-1), 1 part of neopelex shone ultrasound wave 30 minutes, obtained dispersion liquid.This dispersion liquid 70ml is filled in the chamber (volume 100ml) of immersion type laser ablation sampling system [nara machinery is made institute's corporate system], in dispersion liquid, place the block 2g of teflon, to this block irradiating laser (condition wavelength: 270nm, output: 60mJ/pulse) 15 minutes, make the surface of teflon evaporation at spherical Titanium particles (LB-1).With regard to 2 layers of structure spherical particle (LB-12), the dispersion liquid in the chamber is carried out carrying out drying after centrifuging, the washing, obtain { volume average particle size 2.7 μ m, average circularity 0.98} thus.

＜Production Example 8 〉

Laser irradiation time was changed to " 20 minutes " from 15 minutes, in addition, similarly carry out, obtain 2 layers of structure spherical particle (LB-15) { volume average particle size 2.7 μ m, average circularity 0.98} with Production Example 7.

＜Production Example 9 〉

Laser irradiation time is changed to " 30 minutes " from " 15 minutes ", in addition, similarly carry out, obtain 2 layers of structure spherical particle (LB-18) { volume average particle size 2.7 μ m, average circularity 0.98} with Production Example 7.

＜Production Example 10 〉

(1) in the container that can reduce pressure, puts into 50 parts of spherical Titanium particles (LB-1), heat this container to 100 ℃, be decompressed to-0.2MPa, keep 20.

(2) make container inner pressure be-0.05MPa by nitrogen (99.999%), trimethyl aluminium is full of in the container until reaching 0MPa.After 100 ℃ keep 1 minute, be decompressed to once more-0.2MPa.Reach after the 0MPa by nitrogen, be decompressed to-0.2MPa, reach-0.05MPa, water vapor is full of in the container until reaching 0MPa by nitrogen.After 100 ℃ keep 5 minutes, be decompressed to once more-0.2MPa.

(3) operation of repetition (2) is 135 times, and cooling obtains 2 layers of structure spherical particle of titanium dioxide-aluminum oxide (LB-21) { volume average particle size 2.7 μ m, average circularity 0.98}.

＜Production Example 11 〉

" operation of repetition (2) 135 times " changed to " operation of repetition (2) 165 times ", in addition, similarly carry out, obtain 2 layers of structure spherical particle (LB-24) { volume average particle size 2.7 μ m, average circularity 0.98} with Production Example 10.

＜Production Example 12 〉

" operation of repetition (2) 135 times " changed to " operation of repetition (2) 190 times ", in addition, similarly carry out, obtain 2 layers of structure spherical particle (LB-27) { volume average particle size 2.7 μ m, average circularity 0.98} with Production Example 10.

＜Production Example 13 〉

800 parts of ion exchange waters and neopelex are evenly mixed for 5 parts, obtain water.On the other hand, the 15 parts of evenly mixing of reactive surfactant { ELEMINOL JS-2: Sanyo changes into industrial group's system } with 180 parts of styrene, 5 parts of azo dibutyronitriles, anionic property obtain oil reservoir.Then, add oil reservoir to the aqueous phase full dose, use rotor-stator type dispersion machine [TK homogenizer: special machine chemical industry corporate system], after 4000rpm stirring 1 minute, move to pressure vessel with stirring apparatus, 85 ℃ of reactions 12 hours, obtain containing the dispersion liquid of spherical resin particle (LB-30).With regard to spherical resin particle (LB-30), dispersion liquid is carried out carrying out drying after centrifuging, the washing, obtain { volume average particle size 5.3 μ m, average circularity 0.98} thus.

＜Production Example 14 〉

After the mixed liquor of 900 parts of ion exchange waters, 50 parts on spherical resin particle (LB-30) irradiation ultrasound wave 30 minutes, add 3 parts of the reactive surfactants (S-1) of cationic, stirred 4 hours, obtain dispersion liquid.On the other hand, after 0.03 part of reactive surfactant [ELEMINOL JS-2: Sanyo changes into industrial group's system] and 0.01 part of even mixing of azo dibutyronitrile with 0.47 part of methyl methacrylate, anionic property, this mixed liquor is added in the dispersion liquid, stirred 30 minutes, and obtained mixed dispersion liquid.Mixed dispersion liquid is moved to after the pressure vessel with stirring apparatus,, obtain containing the dispersion liquid of 2 layers of structure spherical particle (LB-31) 85 ℃ of reactions 12 hours.With regard to 2 layers of structure spherical particle (LB-31), this dispersion liquid is carried out carrying out drying after centrifuging, the washing, obtain { volume average particle size 5.3 μ m, average circularity 0.98} thus.

＜Production Example 15 〉

Methyl methacrylate is changed to " 0.55 part " from " 0.47 part ", in addition, similarly carry out, obtain 2 layers of structure spherical particle (LB-34) { volume average particle size 5.3 μ m, average circularity 0.98} with Production Example 14.

＜Production Example 16 〉

Methyl methacrylate is changed to " 0.68 part " from " 0.47 part ", in addition, similarly carry out, obtain 2 layers of structure spherical particle (LB-37) { volume average particle size 5.4 μ m, average circularity 0.98} with Production Example 14.

＜embodiment 1 〉

0.2 part, the 2 layers structure spherical particle of reactive surfactant (S-1) (LB-3) of 800 parts of ion exchange waters, cationic are evenly mixed for 50 parts, obtain dispersion liquid.On the other hand, the reactive surfactant { ELEMINOL JS-2: Sanyo changes into industrial group's system } of 0.2 part of styrene, 0.17 part of divinylbenzene, 0.1 part of hydroxyethyl methylacrylate, 0.03 part of azo dibutyronitrile and anionic property is evenly mixed for 0.2 part, obtain oil reservoir.Then, heating dispersion liquid to 85 ℃, with 1 hour under agitation after wherein dripping oil reservoir, reacted 12 hours, obtain containing the dispersion liquid of 3-tier architecture spherical resin particle (LB-4).With regard to 3-tier architecture spherical particle (LB-4), to this dispersion liquid carry out centrifuging, the washing after, carry out drying, obtain { 3-tier architecture of crosslinked polystyrene-monox-crosslinked polystyrene, volume average particle size 5.4 μ m, average circularity 0.98} thus.

＜embodiment 2 〉

" spherical resin particle (LB-2) " is altered to " 3-tier architecture spherical particle (LB-4) ", in addition, similarly carry out with Production Example 4, obtain after 4 layers of structure spherical particle, " 2 layers of structure spherical particle (LB-3) " are altered to " 4 layers of structure spherical particle ", in addition, carry out similarly to Example 1, obtain 5 layers of structure spherical particle.Then, change " sandwich construction spherical particle ", in addition, with Production Example 4 and embodiment 1 similarly alternate repetition carry out, obtain having 23 layers of structure spherical particle (LB-5) { volume average particle size 10.2 μ m, the average circularity 0.99} of crosslinked polystyrene layer-silicon oxide layer thus.

＜embodiment 3 〉

" 2 layers of structure spherical particle (LB-3) " are altered to " 2 layers of structure spherical particle (LB-6) ", styrene is altered to " 0.24 part " from " 0.2 part ", divinylbenzene is altered to " 0.20 part " from " 0.17 part ", hydroxyethyl methylacrylate is altered to " 0.11 part " from " 0.1 part ", in addition, carry out similarly to Example 1, obtain 3-tier architecture spherical particle (LB-7) { volume average particle size 5.4 μ m, average circularity 0.98}.

＜embodiment 4 〉

" 2 layers of structure spherical particle (LB-3) " are altered to " 3-tier architecture spherical particle (LB-7) ", in addition, similarly carry out with Production Example 5, obtain after 4 layers of structure spherical particle, " 2 layers of structure spherical particle (LB-3) " are altered to " 4 layers of structure spherical particle ", styrene is altered to " 0.24 part " from " 0.2 part ", divinylbenzene is altered to " 0.20 part " from " 0.17 part ", hydroxyethyl methylacrylate is altered to " 0.11 part " from " 0.1 part ", in addition, carry out similarly to Example 1, obtain 5 layers of structure spherical particle.Then, change " sandwich construction spherical particle ", with above-mentioned the same styrene, divinylbenzene and the hydroxyethyl methylacrylate of changing, in addition, with Production Example 5 and embodiment 1 similarly alternate repetition carry out, obtain 23 layers of structure spherical particle (LB-8) { volume average particle size 11.2 μ m, average circularity 0.99} thus.

＜embodiment 5 〉

" 2 layers of structure spherical particle (LB-3) " are altered to " 2 layers of structure spherical particle (LB-9) ", styrene is altered to " 0.29 part " from " 0.2 part ", divinylbenzene is altered to " 0.24 part " from " 0.17 part ", hydroxyethyl methylacrylate is altered to " 0.15 part " from " 0.1 part ", in addition, carry out similarly to Example 1, obtain 3-tier architecture spherical particle (LB-10) { volume average particle size 5.6 μ m, average circularity 0.98}.

＜embodiment 6 〉

" 2 layers of structure spherical particle (LB-3) " are altered to " 3-tier architecture spherical particle (LB-10) ", in addition, similarly carry out with Production Example 6, obtain after 4 layers of structure spherical particle, " 2 layers of structure spherical particle (LB-3) " are altered to " 4 layers of structure spherical particle ", styrene is altered to " 0.29 part " from " 0.2 part ", divinylbenzene is altered to " 0.24 part " from " 0.17 part ", hydroxyethyl methylacrylate is altered to " 0.15 part " from " 0.1 part ", in addition, carry out similarly to Example 1, obtain 5 layers of structure spherical particle.Then, change " sandwich construction spherical particle ", with above-mentioned the same styrene, divinylbenzene and the hydroxyethyl methylacrylate of changing, in addition, with Production Example 6 and embodiment 1 similarly alternate repetition carry out, obtain 23 layers of structure spherical particle (LB-11) { volume average particle size 12.2 μ m, average circularity 0.99} thus.

＜embodiment 7 〉

" spherical Titanium particles (LB-1) " is altered to " 2 layers of structure spherical particle (LB-12) ", " teflon " is altered to " titanium dioxide ", in addition, similarly carry out with Production Example 7, obtain 3-tier architecture spherical particle (LB-13) { volume average particle size 2.7 μ m, average circularity 0.98}.

＜embodiment 8 〉

" spherical Titanium particles (LB-1) " is altered to " 3-tier architecture spherical particle (LB-13) ", in addition, similarly carry out with Production Example 7, obtain after 4 layers of structure spherical particle, " spherical Titanium particles (LB-1) " is altered to " 4 layers of structure spherical particle ", and " teflon " is altered to " titanium dioxide ", in addition, similarly carry out with Production Example 7, obtain 5 layers of structure spherical particle.Then, change " sandwich construction spherical particle ", and alternately change " teflon " and " titanium dioxide ", in addition, carry out repeatedly and Production Example 7 identical operations, obtain alternately laminated 10 layers of structure spherical particle (LB-14) { volume average particle size 3.1 μ m, the average circularity 0.99} that titanium oxide layer-polytetrafluoroethylene floor is arranged thus.

＜embodiment 9 〉

" spherical Titanium particles (LB-1) " is altered to " 2 layers of structure spherical particle (LB-15) ", " teflon " is altered to " titanium dioxide ", and laser irradiation time is altered to " 20 minutes " from " 15 minutes ", in addition, similarly carry out with Production Example 7, obtain 3-tier architecture spherical particle (LB-16) { volume average particle size 2.8 μ m, average circularity 0.98}.

＜embodiment 10 〉

" spherical Titanium particles (LB-1) " is altered to " 3-tier architecture spherical particle (LB-16) ", and laser irradiation time is altered to " 20 minutes " from " 15 minutes ", in addition, similarly carry out with Production Example 7, obtain after 4 layers of structure spherical particle, " spherical Titanium particles (LB-1) " is altered to " 4 layers of structure spherical particle ", " teflon " is altered to " titanium dioxide ", and laser irradiation time is altered to " 20 minutes " from " 15 minutes ", in addition, similarly carry out with Production Example 7, obtain 5 layers of structure spherical particle.Then, change " sandwich construction spherical particle ", laser irradiation time is altered to " 20 minutes " from " 15 minutes ", and alternately change " teflon " and " titanium dioxide ", in addition, carry out repeatedly and Production Example 7 identical operations, obtain 10 layers of structure spherical particle (LB-17) { volume average particle size 3.5 μ m, average circularity 0.99} thus.

＜embodiment 11 〉

" spherical Titanium particles (LB-1) " is altered to " 2 layers of structure spherical particle (LB-18) ", " teflon " is altered to " titanium dioxide ", and laser irradiation time is altered to " 30 minutes " from " 15 minutes ", in addition, similarly carry out with Production Example 7, obtain 3-tier architecture spherical particle (LB-19) { volume average particle size 2.9 μ m, average circularity 0.98}.

＜embodiment 12 〉

" spherical Titanium particles (LB-1) " is altered to " 3-tier architecture spherical particle (LB-19) ", and laser irradiation time is altered to " 30 minutes " from " 15 minutes ", in addition, similarly carry out with Production Example 7, obtain after 4 layers of structure spherical particle, " spherical Titanium particles (LB-1) " is altered to " 4 layers of structure spherical particle ", " teflon " is altered to " titanium dioxide ", and laser irradiation time is altered to " 30 minutes " from " 15 minutes ", in addition, similarly carry out with Production Example 7, obtain 5 layers of structure spherical particle.Then, change " sandwich construction spherical particle ", laser irradiation time is altered to " 30 minutes " from " 15 minutes ", and alternately change " teflon " and " titanium dioxide ", in addition, carry out repeatedly and Production Example 7 identical operations, obtain 10 layers of structure spherical particle (LB-20) { volume average particle size 4.0 μ m, average circularity 0.99} thus.

＜embodiment 13 〉

" spherical Titanium particles (LB-1) " is altered to " 2 layers of structure spherical particle (LB-21) ", " trimethyl aluminium " is altered to " chloride oxidation titanium (salt チ ニ ア) ", in addition, similarly carry out obtain having titanium oxide layer-alumina layer-the 3-tier architecture spherical particle (LB-22) of titanium oxide layer { volume average particle size 2.7 μ m, average circularity 0.98} with Production Example 10.

＜embodiment 14 〉

" spherical Titanium particles (LB-1) " is altered to " 3-tier architecture spherical particle (LB-22) ", in addition, similarly carry out with Production Example 10, obtain after 4 layers of structure spherical particle, " spherical Titanium particles (LB-1) " is altered to " 4 layers of structure spherical particle ", and " trimethyl aluminium " is altered to " chloride oxidation titanium ", in addition, similarly carry out with Production Example 10, obtain 5 layers of structure spherical particle.Then, change " sandwich construction spherical particle ", and alternately change " trimethyl aluminium " and " chloride oxidation titanium ", in addition, carry out repeatedly and Production Example 10 identical operations, obtain 10 layers of structure spherical particle (LB-23) { volume average particle size 3.1 μ m, average circularity 0.98} thus.

＜embodiment 15 〉

" spherical Titanium particles (LB-1) " is altered to " 2 layers of structure spherical particle (LB-24) ", " trimethyl aluminium " is altered to " chloride oxidation titanium ", reach " operation of repetition (2) 135 times " is altered to " operation of repetition (2) 165 times ", in addition, similarly carry out with Production Example 10, obtain 3-tier architecture spherical particle (LB-25) { volume average particle size 2.8 μ m, average circularity 0.98}.

＜embodiment 16 〉

" spherical Titanium particles (LB-1) " is altered to " 3-tier architecture spherical particle (LB-25) ", reach " operation of repetition (2) 135 times " is altered to " operation of repetition (2) 165 times ", in addition, similarly carry out with Production Example 10, obtain after 4 layers of structure spherical particle, " spherical Titanium particles (LB-1) " is altered to " 4 layers of structure spherical particle ", " trimethyl aluminium " is altered to " chloride oxidation titanium ", reach " operation of repetition (2) 135 times " is altered to " operation of repetition (2) 165 times ", in addition, similarly carry out with Production Example 10, obtain 5 layers of structure spherical particle.Then, change " sandwich construction spherical particle ", and alternately change " trimethyl aluminium " and " chloride oxidation titanium ", in addition, carry out repeatedly and Production Example 10 identical operations, obtain 10 layers of structure spherical particle (LB-26) { volume average particle size 3.5 μ m, average circularity 0.99} thus.

＜embodiment 17 〉

" spherical Titanium particles (LB-1) " is altered to " 2 layers of structure spherical particle (LB-27) ", " trimethyl aluminium " is altered to " chloride oxidation titanium ", reach " operation of repetition (2) 135 times " is altered to " operation of repetition (2) 190 times ", in addition, similarly carry out with Production Example 10, obtain 3-tier architecture spherical particle (LB-28) { volume average particle size 2.9 μ m, average circularity 0.98}.

＜embodiment 18 〉

" spherical Titanium particles (LB-1) " is altered to " 3-tier architecture spherical particle (LB-28) ", reach " operation of repetition (2) 135 times " is altered to " operation of repetition (2) 190 times ", in addition, similarly carry out with Production Example 10, obtain after 4 layers of structure spherical particle, " spherical Titanium particles (LB-1) " is altered to " 4 layers of structure spherical particle ", " trimethyl aluminium " is altered to " chloride oxidation titanium ", reach " operation of repetition (2) 135 times " is altered to " operation of repetition (2) 190 times ", in addition, similarly carry out with Production Example 10, obtain 5 layers of structure spherical particle.Then, change " sandwich construction spherical particle ", and alternately change " trimethyl aluminium " and " chloride oxidation titanium ", in addition, carry out repeatedly and Production Example 10 identical operations, obtain 10 layers of structure spherical particle (LB-29) { volume average particle size 4.0 μ m, average circularity 0.99} thus.

＜embodiment 19 〉

" spherical resin particle (LB-30) " is altered to " 2 layers of structure spherical particle (LB-31) ", and " methyl methacrylate " is altered to " styrene ", in addition, similarly carry out obtain having polystyrene layer-polymethyl methacrylate layers-the 3-tier architecture spherical particle (LB-32) of polystyrene layer { volume average particle size 5.4 μ m, average circularity 0.98} with Production Example 14.

＜embodiment 20 〉

" spherical resin particle (LB-30) " is altered to " 3-tier architecture spherical particle (LB-32) ", in addition, similarly carry out with Production Example 14, obtain after 4 layers of structure spherical particle, " spherical resin particle (LB-30) " is altered to " 4 layers of structure spherical particle ", and " methyl methacrylate " is altered to " styrene ", in addition, similarly carry out with Production Example 14, obtain 5 layers of structure spherical particle.Then, change " sandwich construction spherical particle ", and alternately change " methyl methacrylate " and " styrene ", in addition, carried out repeatedly and Production Example 14 identical operations, obtained 23 layers of structure spherical particle (LB-33) { volume average particle size 10.2 μ m, average circularity 0.99} thus.

＜embodiment 21 〉

" spherical resin particle (LB-30) " is altered to " 2 layers of structure spherical particle (LB-34) ", and with 0.47 part of methyl methacrylate " be altered to " 0.55 part of styrene "; in addition; similarly carry out, obtain 3-tier architecture spherical particle (LB-35) { volume average particle size 5.4 μ m, average circularity 0.98} with Production Example 14.

＜embodiment 22 〉

" spherical resin particle (LB-30) " is altered to " 3-tier architecture spherical particle (LB-35) ", and will " methyl methacrylate " 0.47 part " is altered to " 0.55 part "; in addition; similarly carry out with Production Example 14; obtain after 4 layers of structure spherical particle; " spherical resin particle (LB-30) " is altered to " 4 layers of structure spherical particle "; and " 0.47 part of methyl methacrylate " is altered to " 0.55 part of styrene ", in addition, similarly carry out with Production Example 14, obtain 5 layers of structure spherical particle.Then, change " sandwich construction spherical particle " is with above-mentioned the same methyl methacrylate and the styrene of changing, in addition, with Production Example 14 similarly alternate repetition carry out, obtain 23 layers of structure spherical particle (LB-36) { volume average particle size 11.2 μ m, average circularity 0.99} thus.

＜embodiment 23 〉

" spherical resin particle (LB-30) " is altered to " 2 layers of structure spherical particle (LB-37) ", and " 0.47 part of methyl methacrylate " is altered to " 0.68 part of styrene ", in addition, similarly carry out with Production Example 14, obtain 3-tier architecture spherical particle (LB-38) { volume average particle size 5.6 μ m, average circularity 0.98}.

＜embodiment 24 〉

" spherical resin particle (LB-30) " is altered to " 3-tier architecture spherical particle (LB-38) ", and methyl methacrylate is altered to " 0.55 part " from " 0.47 part ", in addition, similarly carry out with Production Example 14, obtain after 4 layers of structure spherical particle, " spherical resin particle (LB-30) " is altered to " 4 layers of structure spherical particle ", and " 0.47 part of methyl methacrylate " is altered to " 0.68 part of styrene ", in addition, similarly carry out with Production Example 14, obtain 5 layers of structure spherical particle.Then, change " sandwich construction spherical particle " is with above-mentioned the same methyl methacrylate and the styrene of changing, in addition, with Production Example 14 similarly alternate repetition carry out, obtain 23 layers of structure spherical particle (LB-39) { volume average particle size 12.2 μ m, average circularity 0.99} thus.

About the particle having multilayer structure that in embodiment 1～24, obtains, the volume of the refractive index of the number of plies (n), volume average particle size, average circularity, each layer, central core (L0) gathered be shown in table 1～4.

[table 1]

Annotate) 1. for all silicon oxide layers, average thickness, standard deviation are identical.

2. for all crosslinked polystyrene layers, average thickness, standard deviation are identical.

3. average bed thickness: the mean value of all layers.

[table 2]

Annotate) 1. for all polytetrafluoroethylene floors, average thickness, standard deviation are identical.

2. for all titanium oxide layers, average thickness, standard deviation are identical.

3. average bed thickness: the mean value of all layers.

[table 3]

Annotate) 1. for all alumina layers, average thickness, standard deviation are identical.

2. for all titanium oxide layers, average thickness, standard deviation are identical.

3. average bed thickness: the mean value of all layers.

[table 4]

Annotate) 1. for all polymethyl methacrylate layers, average thickness, standard deviation are identical.

2. for all polystyrene layers, average thickness, standard deviation are identical.

3. average bed thickness: the mean value of all layers.

Volume average particle size, average circularity, average bed thickness, the number of plies (n) and refractive index adopt following method to measure.

(1) evaluation of volume average particle size and average circularity

98 parts of 1 part of hybrid multilayer structure spherical particle, 1 part of neopelex and ion exchange waters, irradiation ultrasound wave 30 minutes, preparation dispersion liquid.Measure the volume average particle size and the average circularity of this dispersion liquid by streaming particle image analytical equipment [Sysmex corporate system: FPIA-3000].

(2) mensuration of average bed thickness, the number of plies (n)

The sandwich construction spherical particle is dispersed in epoxy resin, and { EPIKOTE 828, japan epoxy resin Co., Ltd., " EPIKOTE " are the registered trademarks of Resolution Research Netherland BeslotenVennootschap., after being heating and curing, cut off firming body with little cutter, (TEM) observes its cross section with transmission electron microscope, and each layer measured 10 thickness, calculates its mean value.

The number of plies (n) obtains confirming by observing the cross section.

(3) mensuration of the refractive index of each layer

Under the situation that is resin bed, with spreader coating resin solution, formation determination sample.On the other hand, under the situation that is metal oxide layer, with sol-gel process formation determination sample.

About refractive index, use Abbe refractometer [Atago corporate system: NAR-4T] to measure this film at 25 ℃.

＜comparative example 1～6 〉

With following pigment＜1～3〉or dyestuff＜4～6 particle 1～6 of usefulness as a comparison.

＜1〉C.I. pigment blue 15

＜2〉evenly mix the hybrid pigment that the C.I. pigment yellow 150 of 12 parts C.I. pigment green 36 and 3 parts obtains

＜3〉evenly mix the hybrid pigment that the C.I. paratonere 177 of 10 parts C.I. paratonere 254 and 5 parts obtains

＜4〉dyestuff { acid blue }

＜5〉dyestuff { media is green }

＜6〉dyestuff { acid red }

About the sandwich construction spherical particle that in embodiment 1～24, obtains, estimate color emissivity and transmission light wavelength with following method, it be the results are shown in table 5.In addition, about the spherical particle that obtains in Production Example 2～16, estimate equally, the result is color development not all, does not have summit (peak top).

＜color emissivity 〉

6 parts of 13 parts of mixing pvas [PVA205: Kuraray corporate system], polyvinyl pyrrolidone [PVP-K30: five association's industry corporate systems], 173 parts of methyl alcohol, 211.4 parts in water, estimate 15 parts on sample { sandwich construction spherical resin particle or relatively the particle of usefulness } { dyestuff is 5 parts }, irradiation ultrasound wave 1 hour, the preparation dispersion liquid.With spreader this dispersion liquid is coated on the glass substrate of 50mm * 50mm, making thickness of liquid film is 20 μ m, 80 ℃ of dryings 4 hours, obtains treatment substrate.

From the back side illuminaton of the treatment substrate light from White LED, Visual Confirmation sees through the light of treatment substrate.

＜transmission light wavelength 〉

Use ultraviolet-visible pectrophotometer [Shimadzu Seisakusho Ltd.'s corporate system: UV-2400PC], measure the wavelength that sees through treatment substrate, wherein, the wavelength that will have summit is as the transmission light wavelength.

The treatment substrate for preparing about the particle that uses the multilayer spherical particle obtain and comparative example in embodiment 2 (CF-2), 4 (CF-4), 6 (CF-6), 8 (CF-8), 10 (CF-10) and 12 (CF-12) will be shown in Fig. 1～4 through the wavelength of treatment substrate and the curve map of transmissivity.

[table 5]

＜photostability 〉

The treatment substrate for preparing for the particle that uses the multilayer spherical particle in embodiment 2 (CF-2), 4 (CF-4), 6 (CF-6), 8 (CF-8), 10 (CF-10) and 12 (CF-12), obtain and comparative example, after UV-lamp irradiation ultraviolet radiation 1000 hours, with the above-mentioned the same transmitted light of measuring, will be shown in Fig. 5～8 through the wavelength of treatment substrate and the curve map of transmissivity.

Fig. 3 and Fig. 1, Fig. 2 are compared, and under the situation of having used particle having multilayer structure of the present invention (Fig. 1,2), the wavelength coverage of transmission is narrow, the excitation height as can be known.

Fig. 4 and Fig. 1, Fig. 2 are compared, and under the situation of having used particle having multilayer structure of the present invention (Fig. 1,2), the wavelength coverage of transmission is narrow a little, the excitation height as can be known.

Fig. 7 and Fig. 5, Fig. 6 are compared, do not see the photostability difference.

Fig. 8 and Fig. 5, Fig. 6 are compared, and under the situation of having used particle having multilayer structure of the present invention (Fig. 5,6), photostability is outstanding as can be known.

As mentioned above, sandwich construction spherical particle of the present invention is compared with coloured material (pigment, dyestuff) in the past, and excitation and photostability are obviously outstanding.

＜Production Example 17 〉: the manufacturing of the non-spherical particle of titanium dioxide (central core)

After 20 parts of 200 parts of titanium tetraisopropylates, 750 parts of methyl ethyl ketones, polyvinyl pyrrolidone (number-average molecular weight 40000) are evenly mixed, be heated to 50 ℃, with 2 parts of 30 minutes dropping 1% ammonia spirits.After the dropping, be heated to 80 ℃, reacted 8 hours, obtain containing the dispersion liquid of non-spherical Titanium particles (LB-40).With regard to non-spherical Titanium particles (LB-40), this dispersion liquid is carried out carrying out drying after centrifuging, the washing, obtain { volume average particle size 2.7 μ m, average circularity 0.91} thus.

＜Production Example 18 〉

800 parts of ion exchange waters and neopelex are evenly mixed for 5 parts, obtain water.On the other hand, the 15 parts of evenly mixing of reactive surfactant [ELEMINOL JS-2: Sanyo changes into industrial group's system] with 100 parts of styrene, 80 parts of divinylbenzenes, 5 parts of azo dibutyronitriles and anionic property obtain oil reservoir.Then, add oil reservoir to the aqueous phase full dose, use rotor-stator type dispersion machine [TK homogenizer: special machine chemical industry corporate system], after 4000rpm stirring 1 minute, move to pressure vessel with stirring apparatus, 85 ℃ of reactions 12 hours, obtain containing the dispersion liquid of non-spherical resin particle (LB-41).With regard to non-spherical resin particle (LB-41), after this dispersion liquid being carried out centrifuging, washing, carry out drying, obtain { volume average particle size 5.3 μ m, average circularity 0.92} thus.

＜Production Example 19 〉

50 parts on 900 parts of hybrid ionic exchanged waters and non-spherical resin particle (LB-41) after the irradiation ultrasound wave 30 minutes, add 3 parts of the reactive surfactants (S-1) of cationic, stir 4 hours, obtain dispersion liquid.On the other hand, 0.03 part of the reactive surfactant [ELEMINOL JS-2: Sanyo changes into industrial group's system] and the azo dibutyronitrile of 3 parts of methyl methacrylates, 1.7 parts of divinylbenzenes, anionic property are evenly mixed for 0.2 part, it is added in the above-mentioned dispersion liquid, stirred 30 minutes, and obtained mixed dispersion liquid.This mixed dispersion liquid is moved to the pressure vessel with stirring apparatus,, obtain containing the dispersion liquid of 2 layers of non-spherical particle of structure (LB-42) 85 ℃ of reactions 12 hours.With regard to 2 layers of non-spherical particle of structure (LB-42), this dispersion liquid is carried out carrying out drying after centrifuging, the washing, obtain { volume average particle size 6.3 μ m, average circularity 0.92} thus.

＜Production Example 20 〉

950 parts of hybrid ionic exchanged waters, 45 parts of non-spherical Titanium particles (LB-40) and neopelex mix, and irradiation ultrasound wave 30 minutes obtains dispersion liquid.This dispersion liquid is filled in the chamber of immersion type laser ablation sampling system [nara machinery is made institute's corporate system], place the block of teflon, irradiating laser 3 hours, make the surface of teflon evaporation, obtain containing the dispersion liquid of 2 layers of non-spherical particle of structure (LB-45) in non-spherical Titanium particles (LB-40).With regard to 2 layers of non-spherical particle of structure (LB-45), this dispersion liquid is carried out carrying out drying after centrifuging, the washing, obtain { volume average particle size 3.2 μ m, average circularity 0.91} thus.

＜Production Example 21 〉

10 parts of 550 parts in acetone, 132 parts of diethanolamine, 268 parts of hexamethylene diisocyanates and dibutyl tin laurates are evenly mixed on the limit, the limit was 80 ℃ of reactions 12 hours, add 40 parts of dimethyl suflfates then, and then, obtain the cationic resin solution 50 ℃ of reactions 8 hours.

Then, use rotor-stator type dispersion machine [TK homogenizer: special machine chemical industry corporate system], 500 parts of ion exchange waters are stirred with 8000rpm in the limit, the limit is to wherein adding 500 parts of cationic resin solutions, after stirring 1 minute, acetone { 35 ℃, 12 hours } is heated up in a steamer in decompression, obtains containing dispersion liquid { the volume average particle size 0.03 μ m} of cationic resin particle (EB-1).

＜Production Example 22 〉

Evenly 700 parts of hybrid ionic exchanged waters, 20 parts of neopelexes and ammonium persulfate are 5 parts, as water.On the other hand, evenly 80 parts of benzene mixed ethene, 60 parts of methacrylic acids and methyl methacrylate are 60 parts, obtain oil phase.Then, water is heated to 80 ℃, with 2 hours to wherein dripping oil phase, react after 4 hours, add 2 parts of ammonium persulfates, and then reacted 4 hours, obtain containing dispersion liquid { the volume average particle size 0.04 μ m} of anionic property resin particle (EB-2).

＜Production Example 23 〉

Evenly 800 parts of hybrid ionic exchanged waters and neopelex are 5 parts, obtain water.On the other hand, evenly the reactive surfactant [ELEMINOL JS-2: Sanyo changes into industrial group's system] of 80 parts of benzene mixed ethene, 60 parts of methacrylic acids, 60 parts of methyl methacrylates, 20 parts of divinylbenzenes, 5 parts of azo dibutyronitriles and anionic property is 15 parts, obtains oil reservoir.Then, add oil reservoir to the water full dose, use rotor-stator type dispersion machine [TK homogenizer: special machine chemical industry corporate system], after 4000rpm stirring 1 minute, move to pressure vessel with stirring apparatus, 85 ℃ of reactions 12 hours, obtain containing the dispersion liquid of non-spherical resin particle (LB-48).With regard to non-spherical resin particle (LB-48), this dispersion liquid is carried out carrying out drying after centrifuging, the washing, obtain { volume average particle size 4.1 μ m, average circularity 0.91} thus.

＜Production Example 24 〉

After 1 part of even 700 parts of hybrid ionic exchanged water, 50 parts on non-spherical resin particle (LB-48), 5 parts of NAROACTY N40 (the alkylol ethylene oxide adduct: Sanyo changes into industrial group's system), hydrochloric acid, to wherein adding 50 parts of dispersion liquids containing cationic resin particle (EB-1), stirred 1 hour, and obtained containing the dispersion liquid of 2 layers of non-spherical resin particle of structure (LB-49).With regard to 2 layers of non-spherical resin particle of structure (LB-49), this dispersion liquid is carried out carrying out drying after centrifuging, the washing, obtain { volume average particle size 4.2 μ m, average circularity 0.91} thus.

＜embodiment 25 〉

" non-spherical resin particle (LB-41) " is altered to " 2 layers of non-spherical particle of structure (LB-42) ", and " methyl methacrylate " is altered to " styrene ", in addition, similarly carry out obtain having the crosslinked polystyrene layer-the non-spherical particle of 3-tier architecture (LB-43) of crosslinked polymethylmethacrylaparticles layer-crosslinked polystyrene layer { volume average particle size 7.4 μ m, average circularity 0.92} with Production Example 19.

＜embodiment 26 〉

" non-spherical resin particle (LB-41) " is altered to " the non-spherical particle of 3-tier architecture (LB-43) ", in addition, similarly carry out obtain having polystyrene layer-polymethyl methacrylate layers-polystyrene layer-4 layers of non-spherical particle of structure (LB-44) of methyl methacrylate layer { volume average particle size 8.4 μ m, average circularity 0.93} with Production Example 19.

＜embodiment 27 〉

" non-spherical Titanium particles (LB-40) " is altered to " 2 layers of non-spherical particle of structure (LB-45) ", and " teflon " is altered to " titanium dioxide ", in addition, similarly carry out obtain having titanium oxide layer-polytetrafluoroethylene floor-the non-spherical particle of 3-tier architecture (LB-46) of titanium oxide layer { volume average particle size 4.0 μ m, average circularity 0.92} with Production Example 20.

＜embodiment 28 〉

" non-spherical Titanium particles (LB-40) " is altered to " the non-spherical particle of 3-tier architecture (LB-46) ", in addition, similarly carry out obtain having titanium oxide layer-polytetrafluoroethylene floor-4 layers of non-spherical particle of structure (LB-47) of titanium oxide layer-polytetrafluoroethylene floor { volume average particle size 4.7 μ m, average circularity 0.93} with Production Example 20.

＜embodiment 29 〉

After 5 parts of even 50 parts of 700 parts, 2 layers non-spherical particles of structure of hybrid ionic exchanged water (LB-49), NAROACTY N40 (the alkylol ethylene oxide adduct: Sanyo changes into industrial group's system), to wherein adding 50 parts of dispersion liquids containing anionic property resin particle (EB-2), stirred 1 hour, and obtained containing the dispersion liquid of the non-spherical resin particle of 3-tier architecture (LB-50).With regard to the non-spherical resin particle of 3-tier architecture (LB-50), this dispersion liquid is carried out carrying out drying after centrifuging, the washing, obtain { volume average particle size 4.3 μ m, average circularity 0.92} thus.

＜embodiment 30 〉

" non-spherical resin particle (LB-48) " is altered to " the non-spherical resin particle of 3-tier architecture (LB-50) ", in addition, similarly carry out with Production Example 24, obtain after 4 layers of non-spherical resin particle of structure, " non-spherical resin particle (LB-48) " is altered to " 4 layers of non-spherical resin particle of structure ", and " dispersion liquid that contains cationic resin particle (EB-1) " is altered to " dispersion liquid that contains anionic property resin particle (EB-2) ", in addition, similarly carry out with Production Example 24, obtain 5 layers of non-spherical resin particle of structure.Then, change " sandwich construction spherical particle ", and alternately change " dispersion liquid that contains cationic resin particle (EB-1) " and " dispersion liquid that contains anionic property resin particle (EB-2) ", in addition, carried out repeatedly and Production Example 24 identical operations, obtained 10 layers of non-spherical particle of structure (LB-51) { volume average particle size 4.1 μ m, average circularity 0.93} thus.

About the particle having multilayer structure that in embodiment 25～30, obtains, the volume of the refractive index of the number of plies (n), volume average particle size, average circularity, each layer, central core (L0) gathered be shown in table 6.Need to prove that the refractive index of the number of plies (n), volume average particle size, average circularity and each layer obtains with above-mentioned the samely.

[table 6]

Annotate) 1. for all polymethyl methacrylate layers, average thickness, standard deviation are identical.

2. for all polystyrene layers, average thickness, standard deviation are identical.

3. for all polyvinyl fluoride layers, average thickness, standard deviation are identical.

4. for all titanium oxide layers, average thickness, standard deviation are identical.

5. for all cationic resin beds, average thickness, standard deviation are identical.

6. for all anionic property layers, average thickness, standard deviation are identical.

7. average bed thickness: the mean value of all layers.

For the non-spherical particle of the sandwich construction that obtains in embodiment 25～30, full light transmittance of method evaluation and mist degree with following the results are shown in table 7 with it.Non-spherical particle for obtaining in Production Example 17,18 and 23 carries out identical evaluation.

＜full light transmittance and mist degree 〉

189 parts of mixed methyl methyl acrylates, 1 part of Photoepolymerizationinitiater initiater [IRGNOX1010: Ciba corporate system], evaluation sample { non-spherical particle of sandwich construction or non-spherical particle } 10 parts, irradiation ultrasound wave 5 minutes obtains dispersion liquid.With spreader this dispersion liquid is coated on the glass substrate of 50mm * 50mm, making its thickness of liquid film is 200 μ m, from UV-lamp irradiation ultraviolet radiation 10 seconds, and resin molding (A) thus.

Methyl methacrylate is altered to " 169 parts " from " 189 parts ", and will estimates sample and be altered to " 30 parts " from " 10 parts ", in addition, with the above-mentioned the same resin molding (B) that formed.

Use haze meter NDH2000 (Japanese electric look corporate system), full light transmittance and the mist degree measuring resin molding (A) or (B) { comprise glass substrate }.The evaluation result of resin molding (A) is shown in table 7, the evaluation result of resin molding (B) is shown in table 8.

Need to prove that mist degree is high more, the diffusivity of expression light is high more, and full light transmittance is high more, and the loss of expression light is more little.

[table 7]

[table 8]

Used the resin molding of the non-spherical particle of sandwich construction that in embodiment 25～30, obtains, at the opposite mist degree of original relation and all outstanding aspect two of the light transmittances entirely.On the other hand, the non-spherical particle that in Production Example 17,18,23, obtains, inequality aspect mist degree and full light transmittance two.

Utilize possibility on the industry

Particle having multilayer structure of the present invention, as use in colour filter at display The optical diffusion film that toner, display are used, light diffusing sheet, LGP or antiglare film are exceedingly useful.

Claims (22)

1. a particle having multilayer structure is characterized in that,

Have with central core (L0) serve as nuclear and with respect to nuclear the center with concentric shape stacked more than 2 layers the layer (Ln) structure, the adjacent refringence of layer in the time of 25 ℃ is 0.01～1.5, and at least 1 layer in central core (L0) and the layer (Ln) is metal oxide layer (M).

2. particle having multilayer structure according to claim 1 is characterized in that,

At least 1 layer average thickness is 0.01～3 μ m in the layer (Ln).

3. according to claim 1 or 2 described particle having multilayer structures, it is characterized in that,

The standard deviation of at least 1 layer thickness is below 30% in the layer (Ln).

4. according to any described particle having multilayer structure in the claim 1～3, it is characterized in that,

Volume average particle size is 0.1～20 μ m.

5. according to any described particle having multilayer structure in the claim 1～4, it is characterized in that,

Based on the volume of particle having multilayer structure, the volume of central core (L0) is 5～98 volume %.

6. according to any described particle having multilayer structure in the claim 1～5, it is characterized in that,

At least 1 layer in central core (L0) and the layer (Ln) is resin bed (R), and similarly at least 1 layer is metal oxide layer (M).

7. particle having multilayer structure according to claim 6 is characterized in that,

Resin bed (R) contains cross-linked resin.

8. according to claim 6 or 7 described particle having multilayer structures, it is characterized in that,

Has the alternately laminated structure that resin bed (R) and metal oxide layer (M) are arranged.

9. according to any described particle having multilayer structure in the claim 6～8, it is characterized in that,

Resin bed (R) is at least a kind that selects from polyurethane, polyester, vinylite, fluororesin and polyamide.

10. according to any described particle having multilayer structure in the claim 1～9, it is characterized in that,

Metal oxide layer (M) is at least a kind that selects from monox, aluminium oxide, magnesium oxide, zinc paste and titanium dioxide.

11. according to any described particle having multilayer structure in the claim 1～10, it is characterized in that,

Central core (L0) is metal oxide layer (M).

12. according to any described particle having multilayer structure in the claim 1～11, it is characterized in that,

In at least 1 layer in central core (L0) and layer (Ln), contain at least a kind that from dyestuff, pigment and fluorophor, selects.

13. according to any described particle having multilayer structure in the claim 1～12, it is characterized in that,

Be that average circularity is 0.96～1 spherical particle.

14. according to any described particle having multilayer structure in the claim 1～12, it is characterized in that,

Be that average circularity is more than 0.7 and less than 0.96 non-spherical particle.

15. one kind shows color filter, it is characterized in that,

Used the described particle having multilayer structure of claim 13.

16. a resin molding is characterized in that,

Contain the described particle having multilayer structure of claim 13.

17. a coating material is characterized in that,

Contain the described particle having multilayer structure of claim 13.

18. an optical diffusion film is characterized in that,

Used the described particle having multilayer structure of claim 14.

19. the manufacture method of a particle having multilayer structure is characterized in that, comprising:

From manufacturing process (10), (20), (30) and (40) at least 2 kinds, at least 2 kinds of selection repeatedly or at least a kind repeatedly;

Manufacturing process (10): at the dispersion liquid that is dispersed with central core (L0) (D0) or be dispersed with in the dispersion liquid (Dn) of multilayered particles, place the block of resin or metal oxide, make it produce fine particle to this block irradiated with pulse laser, form resin bed (R) or metal oxide layer (M) on the surface of central core (L0) or multilayered particles thus, obtain the multilayered particles dispersion liquid, thereby obtain particle having multilayer structure;

Manufacturing process (20): have the central core (L0) of reactive group (a) or multilayered particles and gasiform metallic compound that the surface has reactive group (a) react it by heating, surface at central core (L0) or multilayered particles forms metal compound layer, obtain the metal compound layer particle, remove unreacted gasiform metallic compound then, metal compound layer particle and water vapor are reacted, make metal compound layer become metal oxide layer (M), obtain multilayered particles thus, thereby obtain particle having multilayer structure;

Manufacturing process (30): comprise from following operation (31), operation (32), operation (33) and operation (34) select at least a and obtain particle having multilayer structure, promptly

Operation (31): in dispersion liquid (D0) or dispersion liquid (Dn), add metal alkoxide, form metal oxide layer by sol-gel process on the surface of central core (L0) or multilayered particles, obtain the multilayered particles dispersion liquid, described dispersion liquid (D0) is scattered in the alcohol of carbon number 1～4 or the non-protonic solvent (E31) central core (L0) that is made of the resin with active hydrogen and obtains, and the multilayered particles that described dispersion liquid (Dn) makes the surface be made of the resin bed with active hydrogen is scattered in the alcohol of carbon number 1～4 or the non-protonic solvent (E31) and obtains;

Operation (32): to contain can take place that the reactive surfactant (S1) of the cationic of copolymerization or anionic property and surface have the multilayered particles of metal oxide layer with the precursor (m) of resin or the dispersion liquid of the central core (L0) that constitutes by metal oxide in

Copolymerization and the ionic reactive surfactant (S2) opposite with reactive surfactant (S1) and the precursor (m) of resin can take place with the precursor (m) of resin in interpolation, then,

Make the precursor (m) of reactive surfactant (S1), reactive surfactant (S2) and resin that copolymerization take place, form resin bed, obtain the multilayered particles dispersion liquid, the multilayered particles of emanating then on the surface of multilayered particles or central core (L0);

Operation (33): to contain can take place that the reactive surfactant (S1) of the cationic of copolymerization or anionic property and surface have the multilayered particles of resin bed with the precursor (m) of resin or the dispersion liquid of the central core (L0) that constitutes by resin in,

Copolymerization and the ionic reactive surfactant (S2) opposite with reactive surfactant (S1) and the precursor (m) of resin can take place with the precursor (m) of resin in interpolation, then,

Make the precursor (m) of reactive surfactant (S1), reactive surfactant (S2) and resin that copolymerization take place, form resin bed, obtain the multilayered particles dispersion liquid, the multilayered particles of emanating then on the surface of multilayered particles or central core (L0); And

Operation (34): in dispersion liquid (D0) or dispersion liquid (Dn), add metal alkoxide, form metal oxide layer by sol-gel process on the surface of central core (L0) or multilayered particles, obtain the multilayered particles dispersion liquid, described dispersion liquid (D0) is scattered in the alcohol of carbon number 1～4 or the non-protonic solvent (E31) central core (L0) that is made of the metal oxide with active hydrogen and obtains, and the multilayered particles that described dispersion liquid (Dn) makes the surface be made of the metal oxide layer with active hydrogen is scattered in the alcohol of carbon number 1～4 or the non-protonic solvent (E31) and obtains;

Manufacturing process (40): in dispersion liquid (D0) or dispersion liquid (Dn), add metal alkoxide, form metal oxide layer by sol-gel process on the surface of central core (L0) or multilayered particles, obtain the multilayered particles dispersion liquid, thereby obtain particle having multilayer structure, described dispersion liquid (D0) is scattered in the alcohol of carbon number 1～4 or the non-protonic solvent (E31) central core (L0) that is made of resin with active hydrogen or metal oxide and obtains, and the multilayered particles that described dispersion liquid (Dn) makes the surface be made of resin bed with active hydrogen or metal oxide layer is scattered in the alcohol of carbon number 1～4 or the non-protonic solvent (E31) and obtains.

20. the manufacture method of a particle having multilayer structure is characterized in that,

Comprise manufacturing process (50) or manufacturing process (60), promptly

Manufacturing process (50): can take place with the precursor (m) of resin in the dispersion liquid of the cationic of copolymerization or the reactive surfactant (S1) of anionic property and the central core (L0) that constitutes by resin or the surperficial multilayered particles that constitutes by resin bed to containing,

Copolymerization and the ionic reactive surfactant (S2) opposite with reactive surfactant (S1) and the precursor (m) of resin can take place with the precursor (m) of resin in interpolation, then,

Make the precursor (m) of reactive surfactant (S1), reactive surfactant (S2) and resin that copolymerization take place, form resin bed, obtain the multilayered particles dispersion liquid, then on the surface of central core (L0) or multilayered particles

The segregation multilayered particles carries out aforesaid operations repeatedly, obtains particle having multilayer structure;

Manufacturing process, (60): constitute and the surface has electric charge to being dispersed with by resin, (q) central core, (L0) dispersion liquid, (D0) or be dispersed with the surface and constitute and the surface has electric charge by resin bed, the dispersion liquid of multilayered particles (q), (Dn) in, the interpolation particle diameter is a central core, (L0) or the particle diameter of multilayered particles below 1/10th and have and electric charge, (q) opposite electric charge, (r) resin particle, (P0), thus at central core, (L0) or the surface of multilayered particles form by resin particle, (P0) resin bed of Xing Chenging, obtained the multilayered particles dispersion liquid, then

Carry out aforesaid operations repeatedly, obtain particle having multilayer structure.

21. manufacture method according to claim 20 is characterized in that,

In manufacturing process (50), have electric charge (q) on the surface of central core (L0), electric charge (q) is the ionic opposite electric charge with reactive surfactant (S1).

22. according to claim 20 or 21 described manufacture methods, it is characterized in that,

Refringence between the adjacent layer of central core (L0) and formed resin bed in the time of 25 ℃ is 0.01～0.5.

Images