CN101115621A

CN101115621A - Liquid-ejecting head, image-forming apparatus, device for ejecting liquid droplet, and recording method

Info

Publication number: CN101115621A
Application number: CN 200680004525
Authority: CN
Inventors: 上户贵夫
Original assignee: Ricoh Co Ltd
Current assignee: Ricoh Co Ltd
Priority date: 2005-11-11
Filing date: 2006-11-10
Publication date: 2008-01-30
Anticipated expiration: 2026-11-10
Also published as: CN100581821C

Abstract

A liquid ejecting head comprising a nozzle configured to eject a liquid drop of recording liquid, a liquid chamber communicating to the nozzle, and an energy generating device configured to generate energy for pressurizing recording liquid in the liquid chamber is provided, wherein a flow channel forming member configured to form a flow channel for the recording liquid is made of a metal material containing nickel and a peak intensity for a (200) face of nickel is higher than a peak intensity for a (111) face of nickel which intensities are measured by means of X-ray diffraction analysis, or a flow channel forming member configured to form a flow channel for the recording liquid is made of a metal material containing nickel and thallium.

Description

Jet head, imaging device is used for the equipment of liquid droplets and recording method

Technical field

The present invention relates to jet head (liquid ejecting head), imaging device is used for the equipment of liquid droplets and recording method.

Background technology

As imaging device such as printer, facsimile machine, duplicator and its ensemble machine, for example, ink-jet recording apparatus is known.Have jet head as jet recording device by with ink droplet as recording liquid be ejected into the medium that will write down (below be called " paper ", it is not limited to paper as material, but also can be called recording medium, transfer paper, transfer materials and the material that will write down) on and write down (imaging, the image printing, character printing and printing can be used as synonym and use.)。

Simultaneously, as jet head, be known that for example following jet head: have to be used to spray and be of a size of the nozzle of several μ m to the drop of tens of μ m, be communicated to the fluid chamber on the nozzle, have the oscillating plate of element of wall surface of the fluid chamber of being used to form and piezoelectric actuator jet head as the piezoelectric element of the recording liquid that is used for the pressurized fluid body cavity by oscillating plate; Have the nozzle that is used for liquid droplets, be communicated to the fluid chamber on the fluid chamber and be used for jet head according to the hot driver of the recording liquid of phase transformation pressurized fluid body cavity, described phase transformation is caused by the film boiling of using heating to cause; And have the nozzle that is used for liquid droplets, be communicated to the fluid chamber on the nozzle, have the fluid chamber of being used to form wall surface element oscillating plate and utilize oscillating plate and and its electrode of opposite between the electrostatic force that produces be used for the jet head of electrostatic actuator of the recording liquid of pressurized fluid body cavity by mobile oscillating plate.

At this, form element as the nozzle that is used to form nozzle bore (nozzle), as the flow channel formation element that is used to constitute or form the flow channel of jet head, for example provide, as JP-A-2003-025590, JP-A-2004-030636, JP-A-2001-038915 and JP-A-2005-178227 are described, the nozzle of being made by electrocasting by the metal material that comprises nickel forms element, described as JP-2000-318160, form element and described by the nozzle that uses excimer laser punching press organic polymer resin material to obtain as JP 2987954, the nozzle that obtains by the metallic plate that uses the stamping machine punching press to be made by for example SUS forms element.

Simultaneously, form element if be used to form the flow channel of flow channel (flow channel), as nozzle plate, flow passage plate and oscillating plate form by electrocasting, usually be added in the organic additive that has the organic additive of S element in its molecule or have the phenyl ring skeleton, but it is feasible to go wrong, when coated priming paint is heat-treated with in connecting the technology that flow channel forms parts, improve flow channel form the connection performance of element and different elements or be used for forming in its surface oxygen-proof film such as heat oxide film when improving the Technology for Heating Processing of its wettability, cause sulphur fragility and thermal contraction.

When causing this sulphur fragility and thermal contraction, flow channel formation element may be difficult to connect accurately and its productive rate may descend.In addition, when flow channel forms element and is nozzle plate, may go wrong make nozzle bore precise decreasing and may be difficult to obtain its required drop spray characteristic (as function of jet velocity and liquid droplets volume).

Therefore, need provide a kind of jet head of better quality, have the imaging device of this jet head, be used for liquid droplets and have the equipment of this jet head and use the recording method of this jet head.

Summary of the invention

According to an aspect of the present invention, a kind of jet head can be provided, the nozzle that comprises the drop that is configured to injection record liquid, be communicated to the fluid chamber on the nozzle, with be configured to the energy generation apparatus that produce power is used for the recording liquid of pressurized fluid body cavity, the flow channel that wherein is configured to define the flow channel that is used for recording liquid forms that element is made by the metal material that comprises nickel and the peak intensity of (200) face of nickel is higher than the peak intensity of (111) face of nickel, and described intensity is utilized the X-ray diffraction analysis and measured.

According to a further aspect in the invention, a kind of jet head can be provided, the nozzle that comprises the drop that is configured to injection record liquid, be communicated to the fluid chamber on the nozzle, with be configured to the energy generation apparatus that produce power is used for the recording liquid of pressurized fluid body cavity, the flow channel that wherein is configured to define the flow channel that is used for recording liquid forms element and is made by the metal material that comprises nickel and thallium.

According to a further aspect in the invention, can provide imaging device, this imaging device comprises the record head of the drop that is configured to injection record liquid, and wherein record head is aforesaid jet head.

According to a further aspect in the invention, can provide a kind of equipment that is configured to by the jet head liquid droplets, this equipment comprises aforesaid jet head.

According to a further aspect in the invention, can provide a kind of recording method, wherein the drop of recording liquid is sprayed by aforesaid jet head, thereby at the enterprising line item of recording medium.

Description of drawings

Fig. 1 is a decomposition diagram, shows the jet head according to first embodiment of the present invention.

Fig. 2 is a sectional view, shows the jet head longitudinally along fluid chamber.

Fig. 3 is a sectional view, shows along the bipatch structure of the horizontal jet head of fluid chamber.

Fig. 4 is a sectional view, shows along the normal pitch structure of the horizontal jet head of fluid chamber.

Fig. 5 is a plane, shows the nozzle plate of jet head.

Fig. 6 is a sectional view, an example of display element, and wherein nozzle plate and flow passage plate form integral body.

Fig. 7 is a sectional view, an example of display element, and wherein oscillating plate and flow channel form integral body.

Fig. 8 is an overall construction drawing, shows an example of image-forming apparatus according to the present invention.

Fig. 9 is a plane, shows its critical piece.

Figure 10 is a sectional view, shows another example according to jet head of the present invention.

The specific embodiment

Below describe embodiment of the present invention with reference to the accompanying drawings.Jet head according to first embodiment of the present invention is described referring to figs. 1 through 4.At this, Fig. 1 is the decomposition diagram of jet head, and Fig. 2 is a sectional view, shows that along jet head longitudinally and Fig. 3 of fluid chamber be sectional view, shows the horizontal jet head along fluid chamber.

Jet head has the flow passage plate of for example being made by single crystal silicon substrate 1, nozzle plate 2 (being that the nozzle that is connected to the upper surface of channel plate 1 forms element), oscillating plate 3 with the lower surface that is connected to channel plate 1, form the pressurized fluid body cavity 6 that is communicated with the nozzle 4 that is used for liquid droplets by communication passage 5 like this, fluid resistance parts 7, with the connected component 8 that is communicated with fluid chamber 6 by fluid resistance parts 7, and recording liquid (for example, printing ink) is supplied to connected component 8 by the public fluid chamber 10 that forms by the supply hole 9 that forms on oscillating plate 3 in following member 17.

In jet head, each flow passage plate 1, nozzle plate 2 and oscillating plate 3 all are that flow channel forms element, are used to form the flow channel as the printing ink of recording liquid.

Then, corresponding to each pressurized fluid body cavity 6 be connected to the outer surface of oscillating plate 3 as the upper surface of the laminated-type piezoelectric element 12 of driving element (as actuator device and pressure generating equipment) by the connected component that on oscillating plate 3, forms and not have in the drawings to show, this oscillating plate 3 has the element of the wall surface (surfaces on fluid chamber 6 opposites) of formation fluid chamber 6.In addition, the lower surface of laminated-type piezoelectric element 12 is connected to base members (base member) 13.

At this, piezoelectric element 12 is by alternatively laminated piezoelectric material layer 21 and

interior electrode

22a or 22b obtains and be connected to end electrode (external electrode) 23a and 23b respectively by the end face with

interior electrode

22a and 22b, and applies voltage and produce displacement between

end electrode

23a and 23b on laminating direction.

Then, FPC cable 15 utilizes solder flux to connect, ACF (anisotropic conductive film) connects or lead connects and connect and be supplied to piezoelectric element 12 will drive signal, and does not show in the drawings and be provided for optionally the drive circuit (driver IC) that applies drive waveforms to each piezoelectric element 12 and be installed on the FPC cable 15.

In addition, on laterally (in the direction that nozzle 4 is arranged) of fluid chamber, can provide as shown in Figure 3 wherein piezoelectric element 12 and the pillar part 12A bipatch structure of alternately being arranged that as shown in Figure 4 the normal pitch structure that does not have pillar part 12 maybe can be provided.

In this jet head, printing ink in the fluid chamber 6 is by using as the displacement on the d33 direction of the piezoelectricity direction of piezoelectric element 12 and pressurized, in addition, drop sprays according to side ink-jet (side shooter) method, and wherein the direction of liquid droplets is different from the flow direction of recording liquid.Because the side ink ejecting method, the microminiaturization that the size of piezoelectric element 12 is about the size of jet head and piezoelectric element 12 directly causes the microminiaturization of jet head, and its realizes microminiaturization of jet head easily like this.

In addition, the member 17 that forms by injection moulding epoxy resin or poly-(phenylene sulfoether) is connected to by piezoelectric element 12, base members 13, the outer peripheral portion of the drive unit that FPC 15 grades are formed.Then, when above-mentioned public fluid chamber 10 formed on member 17, the supply hole 19 and the supply hole 19 that are formed for recording liquid is supplied to from the outside public fluid chamber 10 further were connected to recording liquid supply source such as secondary groove (sub-tank) and recording liquid cartridge (not shown in FIG.).

At this, flow passage plate 1 is passed through, for example, the use alkaline etch bath body such as potassium hydroxide (KOH) aqueous solution anisotropically etching have the single crystal silicon substrate of (110) high preferred orientation and formation communication passage 5 are provided, through hole (being pressurized fluid body cavity 6), fluid resistance parts 7, connected component 8, the passage component that waits.In addition, the pressurized fluid body cavity separates by partition 6a.

Nozzle plate 2 is formed by nickel (Ni) metallic plate and makes by electroforming (electroforming is moulded) method.The nozzle 4 of diameter 10-35 μ m forms on nozzle plate 2 with corresponding to each pressurized fluid body cavity 6, and described plate uses adhesive to be connected on the flow passage plate 1.Then, nozzle plate 2 carries out the hydrophobic processing on the surface (surface of ejection side: jet face or the face on fluid chamber 6 opposites) of drop ejection side.

Oscillating plate 3 is formed by nickel (Ni) metallic plate and makes by electroforming (electroforming is moulded) method.Corresponding to the part of the oscillating plate 3 of pressurized fluid body cavity 6 is that the thin part of easy deformation and its core have attaching parts and be used to be connected to piezoelectric element 12, and this part is not shown in the drawings.

Piezoelectric element 12 uses by the laminated-type piezoelectric element being connected to base members 13 and passing through subsequently, and for example, cast-cutting saw carries out the passage processing and forms with division.During aforementioned bipatch structure in adopting Fig. 3, pillar part 12A handles the piezoelectric element that forms by passage, but is used as simple pillar, because do not apply driving voltage.

In the jet head of so constructing, for example, when it drives by promotion and striking method, 20-50V driving pulse voltage from the control assembly that does not have in the drawings to show optionally is applied on a plurality of piezoelectric elements 2 according to the image that will write down, the piezoelectric element 12 that applies pulse voltage like this on it be moved so that oscillating plate 3 to the direction distortion of nozzle plate 2, and the volume (capacity) of the liquid in the fluid chamber 6 by fluid chamber 6 change pressurize so that drop from nozzle 4 injections of nozzle plate 2.Then, the pressure of the liquid in the fluid chamber 6 descends along with the injection of liquid, and produces the slight negative pressure that the inertia by liquid flow causes in fluid chamber 6 simultaneously.

Under these conditions, when stopping when piezoelectric element 12 applies voltage, the shape that oscillating plate 3 is back to its home position and fluid chamber 6 is an original-shape, produces bigger negative pressure like this.At this moment, be filled in the fluid chamber 6, and drop is according to spraying from nozzle 4 with after-applied driving pulse from the recording liquid of public fluid chamber 10.

In addition, jet head can not only drive by aforementioned promotion and striking method, but also can for example pass through, stretch and striking method (method that the restoring force that discharges from its stretching attitude owing to oscillating plate 3 is used to pressurize) and stretching, promote and striking method (keep oscillating plate 3 to mediate, subsequently it is stretched from this position and the method for promotion) and driving.

Below describe a kind of flow channel that is respectively in the jet head and form the nozzle plate 2 of element and the details of oscillating plate 3.

Nozzle plate 2 and oscillating plate 3 are made and are passed through electrocasting by the metal material that comprises nickel and thallium and form.The content of thallium is not more than 1% quality of Ni electroforming film and especially preferred, is not more than its 0.01% quality.As described below, may need thallium to be higher than the configuration of peak intensity of (111) face of nickel with the peak intensity that (200) face that makes nickel is provided, described intensity is utilized the X-ray diffraction analysis and is measured, but it is preferred, the content of thallium is not more than 1% quality, because thallium is not preferred for providing glossiness and may be difficult to keep its pH within the required range.In this scope, can easily keep balance with another material that is used for the electroforming bath.

Describe by electrocasting (electroforming molding process) manufacturing nozzle plate 2 as reference Fig. 5, nozzle plate 2 is the electroforming coatings 33 that obtain by following steps: have the element of electric conductivity on its surface at least, for example, electroforming supports base material 31 as forming the pattern 32 of electric insulation coating layer such as dry etching film (DRF) on the silicon substrate that is formed with the Ti film in its surface, in bathing, electroforming on the surface of conduction support base material 31, carries out Ni, Ni-Co, the electroforming of Ni-Mn etc. is with deposition and form electroforming coating 33, remove the pattern 32 of electric insulation coating layer, and further support base material 31 to separate electroforming coating (electroforming film) 33 from electroforming.

In addition, oscillating plate 3 is made by electrocasting similarly and oscillating plate is repeatedly to support on the base material through the electroforming coating of above formation once in electroforming.

Bathe as the electroforming that is used for this electrocasting, use the sulfamic acid salt bath usually and add polishing material (as 1,3,6-naphthalene trisulfonic acid sodium and asccharin), anodic solution agent (as nickel chloride and nickelous bromide) and pH buffer are so that the crystal microminiaturization is given gloss and minimizing stress to the electroforming film.Usually, preferably, the temperature that electroforming is bathed is that about 50 degrees centigrade and current density are 1-10A/dm ²

The anodic solution agent is used for removing, and for example, is used for the oxide-film of the Ni pearl of anode.Use boric acid or formic acid, because electroforming is preferably carried out usually under pH4-6.

For example, can provide to comprise the 200-400g/L nickel sulfamic acid yellowish-brown Ni electrolyte of 0-10g/L nickel chloride and 30g/L boric acid.Add 1,3,6-naphthalene trisulfonic acid sodium or asccharin make that the content of sulphur in Ni electroforming film is 0.1% quality or lower.Then, preferably, sulfur content as far as possible near zero to suppress sulphur fragility and preferably, sulfur content is 0.01% quality or lower.

In addition,, thallium bathes cobalt that nozzle plate 2 and oscillating plate 3 can be by adding cobaltous sulfate or sulfamic acid manganese form or manganese and make by the metal material that comprises nickel and cobalt or nickel and manganese although being added into the Ni electroforming in this article as mentioned above.

In this case, preferably, the cobalt that is added or the content of manganese are not more than 1% quality of Ni electroforming film and particularly preferably are, and it is not more than 0.1% quality of Ni electroforming film.

The cobalt of appropriate amount or manganese are considered to suppress sulphur fragility when heat treatment, and think in addition, produce sulphur-manganese compound or sulphur-cobalt compound, but may need very high current density with sedimentation manganese or cobalt on Ni electroforming film and shortcoming may occur as reducing toughness and increasing the degree of heat-shrinkage that heat treatment was caused.On the other hand, when the manganese that adds or cobalt with respect to the amount of sulphur hour, may be difficult to suppress embrittlement.

Because the standard electrode EMF of above-mentioned thallium is compared relative standard electrode EMF near Ni with cobalt with manganese, thallium can be deposited also even be used for lower current densities effectively.

At this, make the x-ray diffraction intensity of the electroforming film (practical embodiments 1) that comprises thallium under these conditions and the electroforming film (Comparative Examples 1 and 2) that does not contain thallium and made electroforming film and measure by using the X-ray diffraction device.Because the peak intensity of (111) face of the nickel that is recorded by the X-ray diffraction analysis is expressed as the peak intensity of (200) face of I (111) and nickel and is expressed as I (200), so the volume efficiency of orientation crystal face (being defined as the ratio of peak intensity of (111) face of the peak intensity of (200) face of nickel and nickel) is expressed as I (200)/I (111).In addition, for each electroforming film, measure its degree of heat-shrinkage and Vickers hardness thereof when heat-treating.The result of these measurements provides in table 1.

Table 1

	The electroforming film	Heat treatment	I(200)/I(111)	Vickers hardness (HV)	Degree of heat-shrinkage
	The electroforming film	Heat treatment	I(200)/I(111)	Vickers hardness (HV)	Degree of heat-shrinkage	Embodiment
1	The Ni+ thallium	-	9.09	317.0	-
		-	9.09	317.0	-		350℃	4.76	316.0	23ppm
		Comparative Examples 1	Ni	-	0.64	480.7	350℃	4.76	316.0	23ppm	-
275℃	0.48			-	0.64	480.7	368.7	254ppm			-
275℃	0.48			Comparative Examples 2	Ni	-	368.7	254ppm	0.33	469.2	-
350℃	0.19	315.0	432ppm			-			0.33	469.2	-
350℃	0.19	315.0	432ppm			Comparative Examples 3	Ni	-	0.33	505.0	-
350℃	0.09	270.0	540ppm					-	0.33	505.0	-

As can be seen from Table 1, the electroforming film that comprises nickel and thallium has crystalline orientation and makes the peak intensity of (200) face of nickel be higher than the peak intensity of (111) face of nickel.Especially, the Ni electroforming film of the I if volume efficiency satisfies condition (200)/I (111) 〉=3.0 was heat-treated under 350 degrees centigrade 1 hour, its Vickers hardness is less or do not change and the degree of shrinkage (thermal contraction degree) before and after the heat treatment is 23ppm, so not or less generation embrittlement and be not easy to take place thermal contraction.

On the other hand, under 275 degrees centigrade, do not heat-treat 1 hour if do not contain the aforementioned Ni electroforming film of thallium (, cobalt or manganese), the variation of its Vickers hardness greater than 20% and its degree of heat-shrinkage greater than 200ppm.In addition, if under 350 degrees centigrade, heat-treated 1 hour, the variation of its Vickers hardness greater than 30% and its degree of heat-shrinkage greater than 400ppm.Therefore, Ni electroforming film becomes fragile and the flow channel that can not obtain having high size-precision forms element.

Therefore, if be used to form that the flow channel of the flow channel of recording liquid forms that element is made by the metal material that comprises nickel and the peak intensity of (200) face of nickel is higher than the peak intensity of (111) face of nickel, described intensity is utilized the X-ray diffraction analysis and is measured, the sulphur embrittlement can be suppressed and can reduce caused embrittlement and thermal contraction in Technology for Heating Processing so, can realize comprising Technology for Heating Processing so accurately with being connected of another element.

In addition, oxygen-proof film (as ink resistance liquid contact membranes), for example, heat-treat the heat oxide film that obtains on the surface of the contact history liquid by forming element at flow channel, can under flow channel forms element and not have the situation of contraction or embrittlement, form.Like this, can obtain having the jet head of excellent drop spray characteristic.In addition, because Vickers hardness is less or do not descend, exists less or do not have warpage (stress), connection can be carried out accurately like this.

In addition, if being used to form the flow channel formation element of the flow channel of recording liquid is made by the metal material that comprises nickel and thallium, so can be easily forming flow channel under the situation that does not increase current density forms element and makes the peak intensity of (200) face of nickel be higher than the peak intensity of (111) face of nickel, described intensity is utilized the X-ray diffraction analysis and is measured, and the jet head that has excellent drop spray characteristic like this can obtain with high accuracy as mentioned above.

Then,, can improve the precision of nozzle diameter, and the thermal contraction that causes by heat treatment is little if the present invention is applied to nozzle plate.In addition, if the present invention is applied to oscillating plate, the components accuracy of oscillating plate can be improved, and the thermal contraction that causes by heat treatment is little.In addition, although having described the present invention in previous embodiments is applied to form the nozzle plate of element and an example of oscillating plate as flow channel, the present invention also can be applicable to flow passage plate, flow passage plate can obtain accurately like this, and the thermal contraction that causes by heat treatment simultaneously is little and do not use expensive material such as silicon.

In addition, for example, wherein nozzle plate and flow passage plate form whole element 41 or wherein oscillating plate 53 and flow passage plate 52 form whole element 61 can be as shown in Figure 6, forms element and obtain by form flow channel according to electrocasting, and the present invention can be applicable to this class component.Because this configuration, the heat treated degree that is used to connect can reduce and can realize that cost descends.

Followingly describe an example of imaging device with reference to Fig. 8 and 9, this imaging device comprises the equipment that is used for liquid droplets according to of the present invention, and this equipment has according to jet head of the present invention.At this, Fig. 8 is a side view, shows the total of imaging device, and Fig. 9 is a plane, the critical piece of display unit.

Imaging device comprises guide rod 101 and guide rail 102, they are the director elements that extend between the right side and left plate (not shown in FIG.) and supported by above-mentioned side plate, and at main scanning direction fixing balladeur train (carriage) 103 slidably, described balladeur train use on drive pulley 106A that drives by main scanning engine 104 and follow-up pulley 106B, extend be with 105 to move synchronously to go up scanning in the direction of arrow (main scanning direction).

On balladeur train 103, by spraying each color (as black (K), cyan (C), magenta (M) and yellow (Y)) four jet head 107k independently of the present invention of drop (ink droplet) of recording liquid, 107c, the record head 107 that 107m and 107y form are arranged on the direction of main scanning direction and to be arranged to the drop injection direction downward.In addition, although use independently jet head in this article, also can use one or more record heads that a plurality of nozzles are used to spray the drop of each color recording liquid that have.In addition, the number of color is not limited thereto with putting in order.

Be used for being installed in balladeur train 103 to secondary groove 108 of each color of record head 107 each color ink of supply.Printing ink is fed in raw material by inking pipe 109 by the major trough (printing ink print cartridge) that does not have in the drawings to show and is supplied to secondary groove 108.

In addition, being used to send into the paper feed parts that are stacked on the medium that will write down (paper) on the folded parts (pressing plate) 111 of pile such as input tray 110 comprises towards crescent control roll (intake roller) 113 and the separating pad 114 made by high coefficient of friction material, this separating pad 114 is used for separating seriatim from pile lamination 111 and sending into paper 112, and this separating pad 114 is pushed to intake roller 113 those sides.

Then, be transferred to transmission part under the record head 107 as the paper 112 that is used for to send into from the paper feed parts, comprise the transport tape 121 that is used for electrostatic attraction and transmission paper 112, be used for and be pressed on the transport tape 121 by the paper 112 that guider 115 is sent into from the paper feed parts and the reverse rollers of transmitting 122, the moving direction that is used for the paper 112 that near normal up sends into about 90 ° of changes makes it be placed on transmission guider 123 on the transport tape 121, is pushed to the pressure roller 125A and forward position (1eading edge) the pressure roller 125B of transport tape 121 sides by pressurizing member 124.In addition, comprise that charging roller 126 is as the charging equipment that is used for the surface charging of transport tape 121.

At this, transport tape 121 is endless belts, on delivery roll 127 and jockey pulley 128, extend, and by use by subscan engine 131 drive be with synchronously 132 and synchronously roller 133 rotation delivery rolls 127 rotate to band direction of rotation (sub scanning direction).In addition, director element 129 is disposed on the position corresponding to the imaging region of record head 107 at transport tape 121 back sides.

Charging roller 126 is placed to the front surface of contact transport tape 121 and the passive rotation and apply the pressure of 2.5N to every end of axle by the rotation of transport tape 121.

In addition, as being used to discharge on it and the paper of the paper 112 of document image is discharged parts, comprise being used to paper separating component that paper 112 is separated with transport tape 121, exit roller 152 by record head 107, another exit roller 153 and being used to stores the discharge paper pallet 154 of discharging paper 112.

In addition, two-sided paper feed unit 155 is detachably connected to its back.Two-sided paper feed unit 155 receives the paper 112 that the transport tape 121 by rotation in the opposite direction transmits rearward and makes its counter-rotating, and it is sent into interval between reverse rollers 122 and the transport tape 121 once more.

In addition, as shown in figure 14, be used to safeguard or the maintenance of the condition of nozzles of recovery record 107 and recover the nonprinting region that mechanism 156 is disposed in a scanning direction side of balladeur train 103.

Safeguard and recover the cap 157 that mechanism 156 comprises the respective nozzle face that is used to cover record head 107, wiper scraper 158 (being a kind of blade element that is used for the wiping nozzle face), with the blank-injection receiver 159 that is used for receiving drop when carrying out blank the injection, wherein drop is not used in record and injected to eliminate the thickening recording liquid.

Below describe and a kind ofly be used for the printing ink of recording method of the present invention as recording liquid, in the method, drop sprays with at the enterprising line item of recording medium (paper) from jet head according to the present invention.

Be used for comprising water, colouring agent and wetting agent at least, and further comprise bleeding agent as required, surfactant and another component according to the printing ink of recording method of the present invention.

At this, the surface tension of printing ink under 25 degrees centigrade is 15-40mN/m, and preferred 20-35mN/m.If surface tension is lower than 15mN/m, nozzle plate (nozzle plate) according to jet head of the present invention is difficult to form ink droplet (particle) by too wetting making, become significantly according to the bleeding on the recording medium of recording method of the present invention being used for, and be difficult to realize the stable injection of printing ink.On the other hand,, may cause printing ink to infiltrate recording medium deficiently, and may go out ready-made pearl (beading) or prolong drying time if greater than 40mN/m.

Surface tension can 25 degrees centigrade down by using, for example, surface tensiometer (CBVP-Z can derive from Kyowa interface science Co., Ltd) and platinum plate and measure.

In addition, as the coloured material of printing ink, can use pigment or dyestuff and can use its mixture.In addition, if use pigment, compare with dyestuff, it is relatively easy to form the high quality graphic with excellent weatherability and resistance to water on plain paper.

[pigment]

As pigment, can preferably use following pigment.In addition, can use the mixture of multiple pigment.

As organic pigment, can provide, for example, azo, phthalocyanine base, anthraquinonyl, quinacridine ketone group, two  piperazine bases, indigo base, thioindigo base, perylene base and isoindoline ketone group pigment, nigrosine, azomethine type pigment, rhodamine B lake pigment, and carbon black.

As inorganic pigment, can provide, for example, iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminium hydroxide, baryta yellow, barba hispanica, cadmium red, chrome yellow, and metal dust.

The particle diameter of pigment is preferably 0.01-0.30 μ m, and if it be 0.01 μ m or lower, but its light fastness variation maybe can be easy to generate emergence (feathering) because particle diameter is near dyestuff.On the other hand,, can cause spray-hole in the printer or plugged filter and be difficult to realize stable injection, consider and stop up or stable injection that 0.01-0.16 μ m is preferred if it is 0.30 μ m or higher.

As the carbon black that is used for black pigment ink, preferred carbon black is made by oven process or channel process (channelmethod) and is had primary particle size 15-40 millimicron, 50-300 square metre/g of BET specific area, DBP oil factor 40-150ml/100g, 0.5-10% volatile component and pH value 2-9.Therefore, for example can use No.2300, No.900, MCF-88, No.33, No.40, No.45, No.52, MA7, MA8, MA100, No.2200B (can derive from Mitsubishi Chemical company), Raven 700, and Raven 5750, and Raven 5250, Raven 5000, and Raven 3500, Raven 1255 (deriving from the Columbian chemical company), Regal 400R, Regal 330R, Regal 660R, MogulL, Monarch 700, Monarch 800, and Monarch 880, and Monarch 900, and Monarch 1000, Monarch 1100, and Monarch 1300, Monarch 1400 (deriving from Cabot company), look is deceived (Colorblack) FW1, and look is deceived FW2, and look is deceived FW2V, look is deceived FW18, and look is deceived FW200, and look is deceived S150, look is deceived S160, and look is deceived S170, and Printex 35, Printex U, Printex V, Printex 140U, Printex140V, special black 6, special black 5, special black 4A and special black 4 (deriving from Degussa), but be not limited thereto.

The object lesson of color pigment below is provided.

As organic pigment, can provide, for example, azo, phthalocyanine base, anthraquinonyl, quinacridine ketone group, two  piperazine bases, indigo base, thioindigo base; perylene base and isoindoline ketone group pigment, nigrosine, azomethine type pigment, rhodamine B lake pigment, and carbon black, and as inorganic pigment, can provide, for example, iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminium hydroxide, baryta yellow, barba hispanica, cadmium red, chrome yellow, and metal dust.

Particularly, below be provided for the following pigment of each color.

An example as the pigment that can be used for Yellow ink can provide, for example, CI pigment yellow 1,2,3,12,13,14,16,17,73,74,75,83,93,95,97,98,114,128,129,151 and 154, but be not limited thereto.

An example as the pigment that can be used for magenta ink can provide, for example, CI paratonere 5,7,12,48 (Ca), 48 (Mn), 57 (Ca), 57:1,112,123,168,184 and 202, but be not limited thereto.

An example as the pigment that can be used for cyan ink can provide, for example, the CI pigment blue 1,2,3,15:3,15:34,16,22 and 60, and CI vat blue 4 and 60, but be not limited thereto.

In addition, for can be used as, the newly formed pigment of the present invention is included in the pigment that is used for each printing ink of the present invention.

Ink mist recording liquid can obtain by using polymeric dispersant or surfactant that above-mentioned pigment is dispersed in the aqueous medium.Dispersant as the powder that is used to disperse this organic pigment can use water-soluble resin commonly used or water soluble surfactant active.

As the object lesson of water-soluble resin, can provide, for example, block copolymer, random copolymer and its salt, described copolymer derive from least two kinds and are selected from following monomer: styrene, styrene derivative, vinyl naphthalene derivative, α, the aliphatic alcohol esters of β-ethylidene unsaturated carboxylic acid, acrylic acid, acrylic acid derivative, maleic acid, maleic acid derivatives, itaconic acid, derivatives from itaconic acid, fumarate, and fumarate derivative.

These water-soluble resins are alkali soluble resins, dissolve in the aqueous solution that wherein is dissolved with alkali, and therein, particularly preferably be, its weight average molecular weight is 3,000-20,000, because can be under the situation that is used for ink mist recording liquid, can advantageously make the viscosity of dispersing liquid reduce and can easily realize disperseing.

In addition, polymeric dispersant and be preferred for obtaining suitable dot diameter from the combination of dispersed color.Reason is unclear fully as yet, but is thought as follows.

Infiltration in recording paper is suppressed by comprising polymeric dispersant.On the other hand, because be suppressed by comprising polymeric dispersant, thereby can sprawl in the horizontal direction reposefully from dispersed color from the gathering of dispersed color.As a result, ink dot is sprawled widely and is thin, can form desirable ink dot like this.

In addition, as the water soluble surfactant active's who can be used as dispersant object lesson, can provide the following table surface-active agent.For example, as anion surfactant, can provide, for example, higher fatty acid salt, alkyl sulfate, alkyl ether sulfate, alkyl sulfate, alkyl aryl ether sulfate, alkylsulfonate, sulfosuccinate, alkylallyl sulfonate, alkylnaphthalene sulfonate, alkylphosphonic, polyoxyethylene alkyl ether phosphate and alkyl allyl ether phosphate.In addition,, can provide as cationic surfactant, for example, alkylamine salt, dialkyl group amine salt, tetraalkylammonium salt, zephiran salt, alkyl pyridine  salt and imidazoline  salt.

In addition,, can provide as amphoteric surfactant, for example, dimethyl alkyl lauryl betaine, alkyl glycine, alkyl two (amino-ethyl) glycine, and imidazolinium betaine.As non-ionic surface active agent, can provide, for example, polyoxyethylene alkyl ether, polyxyethylated allyl ether, polyoxyethylene polyoxypropylene glycol, glyceride, Isosorbide Dinitrate, sucrose ester, the APEO of glyceride, the APEO of Isosorbide Dinitrate, the APEO of sorbitol ester, fatty acid alkanol amides, the polyoxyethylene fatty acid acid amides, amine oxide, and polyoxyethylene alkyl amine.

In addition, pigment can provide dispersibility to it like this with resin-coating with hydrophilic radical or little sealing (microencapsulated).

As applying or little method of sealing water-insoluble pigment, can use any known method with organic polymer.As known method, can provide, for example, chemical manufacturing method, physical manufacturing method, physico-chemical process, and mechanical manufacturing method.Particularly, can provide, for example, the interface polymerization reaction method, the home position polymerization reaction method, submergence cured coated method, cohesion (being separated) method, the submergence seasoning, fusing-dispersion-cooling method, air suspension cladding process, spraying-seasoning, acid intermediate processing, and phase inversion (phaseinversion) emulsification method.

The interface polymerization reaction method be wherein two kinds of monomers or two kinds of reactants separately are dissolved in decentralized photo and the continuous phase and will be on two kinds of material interfaces between it reaction form the method for wall film.The home position polymerization reaction method is that wherein the either side from continuous phase side and nuclear particle side provides liquid or gaseous monomer and catalyst or two kinds of reactive materials to react and to form the method for wall film.Submergence cured coated method be wherein will comprise core material particles the drop of polymer solution by curing agent etc., make it be insoluble to liquid to form the method for wall film.

Cohesion (being separated) method is wherein polymer dispersed liquid (wherein being dispersed with the particle of core) to be separated into coacervate with high polymer concentration (concentrating phase) and the dilute phase method with formation wall film.The submergence seasoning is a kind of like this method: prepare the liquid in the solution that wherein core is dispersed in the wall membrane material, this dispersing liquid is added in the immiscible liquid of continuous phase with dispersing liquid obtaining complex emulsions, and the medium that will dissolve the moisture film material is removed gradually with formation wall film.

Fusing-dispersion-cooling method is a kind of like this method: heat fused is become liquid and heating of the wall membrane material that solidifies and liquefaction under ordinary temp, the particle of core is dispersed in wherein, make them become fine grained, and cool off to form the wall film.Air suspension cladding process is a kind of like this method: the particle of core is floating in gas and in gas stream as powder suspension by fluid bed, and simultaneously with the spraying of the applying liquid of wall membrane material and be blended in wherein to form the wall film.

Spraying-seasoning is a kind of like this method: the stock solution that will be used to seal is sprayed and is contacted with evaporation and drying and volatilizing component with hot blast, forms the wall film like this.The acid intermediate processing is a kind of like this method: at least one anionic group that will comprise the organic polymer compounds of anionic group neutralizes so that water solubility to be provided with alkali compounds, use coloured material in aqueous medium, to mediate, subsequently, use acid compound to neutralize or acidifying so that organic compound precipitation and they are fixed on the coloured material, and last, neutralize and disperse.The Phase inversion emulsification method is a kind of like this method: provide be included in the mixture that has dispersed anionic organic polymer and coloured material in the water as organic solvent mutually in, water is dropped into organic solvent mutually or with in the congenial entry of organic solvent.

Organic polymer (resin) as the material that is used to constitute microcapsules (microcapsule) wall film can provide, for example, and polyamide, polyurethane, polyester, polyureas, epoxy resin, Merlon, carbamide resin, melamine resin, phenolic resin, polysaccharide, gelatin, Arabic gum, dextran, casein, protein, natural rubber, the carboxyl polymethylene, polyvinyl alcohol, PVP, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, cellulose, ethyl cellulose, methylcellulose, NC Nitroncellulose, hydroxy ethyl cellulose, cellulose acetate, polyethylene, polystyrene, (methyl) acrylic acid homopolymers and copolymer, the homopolymers and the copolymer of (methyl) acrylate, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-(methyl) acrylic copolymer, styrene-maleic acid copolymer, mosanom, aliphatic acid, paraffin, beeswax, water wax, hardened tallow, Brazil wax, and albumin.

Wherein, can use organic polymer with anionic group such as carboxylic group or sulfuryl group.In addition, as the nonionic organic polymer, can provide, for example, polyvinyl alcohol, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, the cation ring-opening polymerization polymer of methoxy poly (ethylene glycol) monomethacrylates and its copolymer and 2- azoles quinoline.Especially, have low water solubility and be dissolved in easily in the hot water but be not easy to be dissolved in performance in the cold water by the fully saponified polyvinyl alcohol that obtains, this is especially preferred.

In addition, be used to constitute the microcapsule wall film organic polymer content 1% weight of the soluble coloured material of water such as organic pigment and carbon black or more and 20% weight or lower between.When the content of organic polymer was in above-mentioned scope, the content of organic polymer in capsule was lower, and therefore, and the decline by the pigment coloring performance that causes with the surface of organic polymer coating pigment can be inhibited.If the content of organic polymer is lower than 1% weight, may be difficult to provide the effect of sealing, and on the other hand, if it surpasses 20% weight, the tinctorial property of pigment may descend significantly.In addition, because consider its other performance, the content of organic polymer is preferably the 5-10% weight of the soluble coloured material of water.

That is, expose basically, so the decline of tinctorial property can be inhibited, and on the other hand, a part of coloured material is not exposed but is coated basically, and therefore the effect of coating pigment is provided simultaneously because the part of coloured material is not coated.In addition, consider the manufacturing of capsule, the number-average molecular weight of organic polymer is preferably 2,000 or higher.At this, " exposing basically " do not mean that the part with defective such as pin hole and crack exposes, but expression is by positive exposed state.

In addition, be from pigment dispersion or from dispersed carbon black if be used as the organic pigment of coloured material, even the content of organic polymer in capsule is low relatively, dispersing of pigments also can be improved, and therefore, can obtain enough storage stabilities, this is preferred for the present invention.

In addition, preferably select suitable organic polymer according to little encapsulating method.For example, for the interface polymerization reaction method, polyester, polyamide, polyurethane, PVP, epoxy resin etc. are suitable.For the home position polymerization reaction method, the homopolymers and the copolymer of (methyl) acrylate, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-(methyl) acrylic copolymer, polyvinyl chloride, polyvinylidene chloride, polyamide etc. are suitable.For submergence cured coated method, mosanom, polyvinyl alcohol, gelatin, albumin, epoxy resin etc. are preferred.For condensing method, gelatin, cellulose, casein etc. are suitable.Certainly, any known encapsulating method except that above-mentioned also can be used for obtaining thin and uniform little encapsulated pigment.

If phase inversion method or sour intermediate processing are selected as little encapsulating method, anionic organic polymer is used as organic polymer so that the microcapsule wall film to be provided.The phase inversion method is a kind of like this method: have in water from dispersed or deliquescent anionic organic polymer and coloured material as complex or anionic organic polymer from dispersed organic pigment or self-dispersion type carbon black, coloured material is as from dispersed organic pigment or self-dispersion type carbon black, with the mixture of curing agent be provided as organic solvent mutually and by water is dropped into organic solvent mutually in or organic solvent carried out in the congenial entry from disperseing to carry out little sealing in (Phase inversion emulsification).In the phase inversion method, it is not problem mutually that the excipient of recording liquid or additive are sneaked into the organic solvent that is used for making.Especially, more preferably sneak into the liquid medium that is used for recording liquid, because can directly make the dispersing liquid that is used for recording liquid.

On the other hand, sour intermediate processing is a kind of like this method: the part in the moisture cake that will obtain by the manufacture method that may further comprise the steps or all anionic groups use the alkali compounds neutralization, thereby carry out little sealing; Described manufacture method comprises: will comprise the part of organic polymer of anionic group or all anionic groups and neutralize with alkali compounds, as in aqueous medium, mediating, and use acid compound that pH is controlled to neutrality or acid so that contain the organic polymer precipitation of anionic group and be fixed on the pigment it and coloured material from dispersed organic pigment or self-dispersion type carbon black.Therefore, can produce and comprise the little encapsulated pigment of the thin anion aqueous liquid dispersion body of (comprising many pigment).

In addition,, can provide as being used for aforesaid little solvent of sealing, for example, alkylol such as methyl alcohol, ethanol, propyl alcohol and butanols; Aromatic hydrocarbons such as benzene, toluene and dimethylbenzene; Ester such as methyl acetate, ethyl acetate and butyl acetate; Chlorinated hydrocabon such as chloroform and dichloroethanes; Ketone such as acetone and isobutyl methyl ketone; Ether such as oxolane and two  alkane; With cellosolve such as methyl cellosolve and butyl cellosolve.In addition, the microcapsules of making by said method utilize centrifugation, filter to wait and to separate from solvent and to stir in water and essential solvent and to disperse, to obtain can be used for target record liquid of the present invention.The average particulate diameter of the encapsulated pigment that obtains by said method is preferably 50nm-180nm.

Therefore, pigment adheres to owing to this resinous coat on the object that will print, and can improve the rub resistance of the object that will print like this.

[dyestuff]

As the dyestuff that is used for recording liquid, use and in Colour Index, be divided into acid dyes, direct dyes, basic-dyeable fibre, chemically-reactive dyes and food coloring also have excellent in water resistance and the dyestuff of light fastness.Multiple in these dyestuffs mix use or, if desired, can mix use with another coloured material such as pigment.The addition of this colouring agent makes effect of the present invention not be suppressed.

(a), for example, can use as acid dyes and food coloring

C.I. Indian yellow 17,23, and 42,44,79 and 142,

C.I. azogeramine, 8,13,14,18,26,27,35,37,42,52,82,87,89,92,97,106,111,114,115,134,186,249,254 and 289,

C.I. acid blue 9,29,45,92 and 249,

C.I. acid black 1,2,7,24,26 and 94,

C.I.

edible Huang

3 and 4,

C.I. edible red 7,9 and 14 and

C.I. edible black 1 and 2.

(b), for example, can use as direct dyes

C.I.

direct Huang

1,12,24,26,33,44,50,86,120,132,142 and 144,

It is C.I. directly red 1,4,9,13,17,20,28,31,39,80,81,83,89,225 and 227,

C.I. direct orange 26,29, and 62 and 102,

C I. directly blue 1,2,6,15,22,25,71,76,79,86,87,90,98,163,165,199 and 202 and

C.I. directly deceive 19,22,32,38,51,56,71,74,75,77,154,168 and 171.

(C), for example, can use as basic-dyeable fibre

C.I. basic yellow 1,2, and 11,13,14,15,19,21,23,24,25,28,29,32,36,40,41,45,49,51,53,63,64,65,67,70,73,77,87 and 91,

It is C.I. alkaline red 2,12,13,14,15,18,22,23,24,27,29,35,36,38,39,46,49,51,52,54,59,68,69,70,73,78,82,102,104,109 and 112,

C.I. alkali blue 1,3,5,7,9,21,22,26,35,41,45,47,54,62,65,66,67,69,75,77,78,89,92,93,105,117,120,122,124,129,137,141,147 and 155 and

C.I. basic black 2 and 8.

(d), for example, can use as chemically-reactive dyes

C.I. reactivity deceives 3,4,7,11,12 and 17,

C.I.

reactive Huang

1,5,11,13,14,20,21,22,25,40,47,51,55,65 and 67,

C.I reactive red 1,14,17,25,26,32,37,44,46,55,60,66,74,79,96 and 97 and

C.I. reactive blue 1,2, and 7,14,15,23,32,35,38,41,63,80 and 95.

[additive and physical property that pigment and dyestuff are commonly used]

Preferred water-miscible organic solvent and the coloured material of using is to be provided for having desired physical properties or preventing because the recording liquid drying causes the recording liquid of the obstruction of record head nozzle of image-forming apparatus according to the present invention.Water-miscible organic solvent can comprise wetting agent or bleeding agent.Adding wetting agent is in order to prevent owing to the dry obstruction that causes the record head nozzle of recording liquid.

The object lesson of wetting agent is polyalcohol such as ethylene glycol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, polyethylene glycol, propane diols, 1,3-butanediol, 1, ammediol, 2-methyl isophthalic acid, ammediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexylene glycol, glycerine, 1,2, the 6-hexanetriol, 2-ethyl-1,3-hexylene glycol, 1,2, the 4-butantriol, 1,2,3-butantriol and penta triol; Polyol alkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diglycol monotertiary methyl ether, carbiphene, diglycol monotertiary butyl ether, triethylene glycol single-butyl ether, tetraethylene glycol monomethyl ether and propane diols list ethylether; Polyalcohol aryl ether such as glycol monomethyl phenyl ether and glycol monomethyl benzylic ether; Nitrogen-containing heterocycle compound such as N-N-methyl-2-2-pyrrolidone N-, N-ethoxy-2-Pyrrolidone, 2-Pyrrolidone, 1,3-dimethyl-imidazolinone, and epsilon-caprolactams; Acid amides such as formamide, N-NMF, and N, dinethylformamide; Amine such as MEA, diethanol amine, triethanolamine, mono aminoethane, diethylamine, and triethylamine; Sulfur-containing compound such as dimethyl sulfoxide (DMSO), sulfolane, and thiodiethanol; Propylene carbonate, ethylene carbonate, and gamma-butyrolacton.These solvents are used in combination separately or with water.

In addition, the adding of bleeding agent is for the wettability that improves the material that will write down and recording liquid and regulates its seepage velocity.As bleeding agent, the bleeding agent that is expressed as following structural formula (I)-(IV) is preferred.Promptly, because the polyoxyethylene alkyl phenyl ether type surfactant of following structural formula (I), the acetylenediol type surfactant of following structural formula (II), the polyoxyethylene polyoxy-propylene type surfactant of the polyoxyethylene alkyl ether type surfactant of following structural formula (III) and following structural formula (IV) can reduce the surface tension of liquid, thereby wettability can be improved and seepage velocity can increase.

(R has 6-14 carbon atom and hydrocarbon chain that can have side chain and k are 5-20.)

(m and n are respectively 0-40.)

R-(OCH ₂CH ₂) _nH ……(III)

(R has the hydrocarbon chain of 6-14 carbon atom and m and n to be equal to or less than 20 number.)

Except having the compound of structural formula (I)-(IV), also for example can use polyalcohol alkyl or aryl ether such as diglycol monotertiary phenyl ether, the glycol monomethyl phenyl ether, ethylene glycol monoallyl ether, diglycol monotertiary butyl ether, propane diols single-butyl ether and tetraethylene glycol chlorphenyl ether; Non-ionic surface active agent such as polyoxyethylene polyoxypropylene block copolymer, fluorine-containing surfactant and lower alcohol such as ethanol and 2-propyl alcohol and diglycol monotertiary butyl ether are especially preferred.

But surfactant is not particularly limited and can be according to purposes and suitably select, and for example, can provide anion surfactant, non-ionic surface active agent, amphoteric surfactant, and fluorinated surfactant.

As anion surfactant, can provide, for example, polyoxyethylene alkyl ether acetic acid esters, dodecyl benzene sulfonate, laruate, and polyoxyethylene alkyl ether sulfate salt.

As non-ionic surface active agent, can provide, for example, acetylenediol type surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyxyethylated ester, and polyoxyethylene sorbitan fatty acid ester.

As acetylenediol type surfactant, can provide, for example, and 2,4,7,9-tetramethyl-5-decine-4,7-glycol, 3,6-dimethyl-4-octyne-3,6-glycol and 3,5-dimethyl-1-hexin-3-alcohol.For acetylenediol type surfactant, can provide, for example, Surfynol 104,82,465,485, and TG (can derive from Air Products and Chemicals, Inc.) as commercial product.

As amphoteric surfactant, can provide, for example, lauryl alanine ester, lauryl dimethyl betaine, stearyl dimethyl betaine and lauryl dihydroxy ethyl betaine.In addition, can provide, for example, lauryl dimethyl amine oxide, nutmeg base dimethyl oxidation amine, stearyl dimethyl amine oxide, dihydroxy ethyl lauryl amine oxide, polyoxyethylene coconut oil alkyl dimethyl amine oxide, dimethyl alkyl (coconut) betaine and dimethyl lauryl betaine.

In these surfactants, be expressed as following chemical structural formula (V), (VI), (VII), (VIII), (IX) and surfactant (X) be preferred.

R1-O-(CH ₂CH ₂O)hCH ₂COOM…… (V)

In chemical structural formula (V), R1 is the alkyl group with had side chain of 6-14 carbon atom.H is the integer of 3-12.M is selected from alkali metal ion, quaternary ammonium ion ， quaternary phosphine ion, and alkanolamine.

In chemical structural formula (VI), R ²It is alkyl group with had side chain of 5-16 carbon atom.M is selected from alkali metal ion, quaternary ammonium ion ， quaternary phosphine ion, and alkanolamine.

In chemical structural formula (VII), R ³Be hydrocarbyl group as the alkyl group of had side chain with 6-14 carbon atom.K is the integer of 5-20.

R4-(OCH ₂CH ₂)jOH …… (VIII)

In chemical structural formula (VIII), R ⁴Be that hydrocarbyl group is as having the alkyl group of 6-14 carbon atom.J is the integer of 5-20.

In chemical structural formula (IX), R ⁶Be hydrocarbyl group as the alkyl group of had side chain with 6-14 carbon atom.L and p are respectively the integer of 1-20 independently.

In chemical structural formula (X), q and r are respectively integer 0-40 independently.

Be expressed as above-mentioned chemical structural formula (V) and below the surfactant (VI) particularly the form with free acid provide.At first, as surfactant (V), can provide the following table surface-active agent that is expressed as (V-1) to (V-6).

CH ₃(CH ₂) ₁₂O(CH ₂CH ₂O) ₃CH ₂COOH ……(V-1)

CH ₃(CH ₂) ₁₂O(CH ₂CH ₂O) ₄CH ₂COOH ……(V-2)

CH ₃(CH ₂) ₁₂O(CH ₂CH ₂O) ₅CH ₂COOH ……(V-3)

CH ₃(CH ₂) ₁₂O(CH ₂CH ₂O) ₆CH ₂COOH ……(V-4)

Then, as surfactant (VI), can provide the following table surface-active agent that is expressed as (VI-1) to (VI-4).

As fluorinated surfactant, the surfactant that is expressed as following chemical structural formula (A) is preferred.

CF ₃CF ₂(CF ₂CF ₂)m-CH ₂CH ₂O(CH ₂CH ₂O)nH ……(A)

In chemical structural formula (A), m is the integer of 0-10 and the integer that n is 1-40.

As fluorinated surfactant, can provide, for example, the perfluoro alkyl sulfonic acid compound, perfluoro carboxylic acid compound, perfluoroalkyl phosphate compound, perfluoroalkyl oxirane compound and have the polyoxyalkylene ether polymer of perfluoroalkyl ether group as side chain.Wherein, have the perfluoroalkyl ether group and have low foaming and low fluorine compounds biogenic accumulation possibility (this is considered to problem recently) as the polyoxyalkylene ether polymer of side chain, and be safe therefore, this is especially preferred.

As the perfluoro alkyl sulfonic acid compound, can provide, for example, perfluoro alkyl sulfonic acid and fluorinated alkyl sulfonate.

As the perfluoro carboxylic acid compound, can provide, for example, perfluoro carboxylic acid and perfluoroalkyl carboxylate.

In addition,, can provide as the perfluoroalkyl phosphate compound, for example, derived from the salt of the ester of the ester of perfluoroalkyl phosphoric acid and perfluoroalkyl phosphoric acid.

As having the polyoxyalkylene ether polymer of perfluoroalkyl ether group as side chain, can provide, for example, have the polyoxyalkylene ether polymer of perfluoroalkyl ether group as side chain, has the perfluoroalkyl ether group as the sulfate of the polyoxyalkylene ether polymer of side chain with have the salt of perfluoroalkyl ether group as the polyoxyalkylene ether polymer of side chain.

As the counter ion counterionsl gegenions of the salt in the above-mentioned fluorinated surfactant, can provide, for example, Li, Na, K, NH ₄, NH ₃CH ₂CH ₂OH, NH ₂(CH ₂CH ₂OH) ₂, and NH (CH ₂CH ₂OH) ₃

Fluorinated surfactant can synthesize suitably and use maybe and can use the commercial goods.

As its commercial goods, can provide, for example, Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (can derive from Asahi Glass Co., Ltd.); Fluorad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, and FC-431 (can derive from Sumitomo 3M Limited); Megafac F-470, F1405, and F-474 (can derive from Dainippon printing ink and chemical company); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (can derive from DuPont); FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (can derive from NEOS Co.Ltd.); And PF-151N (can derive from OmnovaSolutions, Inc.).Wherein, Zonyl FSN, FSO-100, and FSO (can derive from DuPont) is being especially preferred aspect high reliability and the good colour development.

Other component is not particularly limited and can suitably selects as required, and can provide, for example, and resin emulsion, pH conditioning agent, anticorrisive agent or bactericide, rust inhibitor, antioxidant, ultra-violet absorber, oxygen absorbent, and light stabilizer.

Resin emulsion obtains in the water as continuous phase and can comprise dispersant such as surfactant as required by the resin thin particle is dispersed in.

Generally, preferably, be the 10-70% quality as the fine grain content of the resin of dispersed phase component (content of resin thin particle in resin emulsion).In addition, about the fine grain particle diameter of resin, average particulate diameter is preferably 10-1, and 000nm, and more preferably 20-300nm especially consider the application in ink-jet recording apparatus.

The fine grain material of resin in the decentralized photo is not particularly limited and can suitably selects according to purposes, and can provide, for example, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, vinyl chloride resin, acrylic compounds-styrene resin and acrylic compounds organic siliconresin.Wherein, the acrylic compounds organic siliconresin is especially preferred.

Resin emulsion can be synthesized suitably and use and maybe can use the commercial goods.

As the commercial resins emulsion, can provide, for example, Microgel E-1002, E-5002 (styrene-propene acid resin emulsion can derive from Nippon paint Co., Ltd); VONCOAT 4001 (acrylic resin emulsion can derive from Dainippon printing ink and chemical company); VONCOAT 5454 (styrene-propene acid resin emulsion can derive from Dainippon printing ink and chemical company); SAE-1014 (styrene-propene acid resin emulsion can derive from ZEON company); Saibinol SK-200 (acrylic resin emulsion can derive from Saiden Chemical Industrial Co., Ltd); Primal AC-22, AC-61 (acrylic resin emulsion can derive from Rohm and Haas Company); Nanocryl SBCX-2821,3689 (acrylic compounds organic siliconresin emulsion can derive from Toyo printing ink Manufacturing Co., Ltd); And #3070 (the methylmethacrylate polymer resin emulsion can derive from Mikuni Color Ltd.).

In the printing ink in the resin emulsion content of added resin thin grain fraction be preferably the 0.1-50% quality, more preferably 0.5-20% quality, and further preferred 1-10% quality.If content is lower than 0.1% quality, the effect that improves anti-obstruction and jetting stability may be insufficient, and if greater than 50% quality, the storage stability possible deviation of printing ink.

Consider simultaneously and satisfy that the surface tension that is used for the recording liquid of image-forming apparatus according to the present invention is preferably 10-60N/m, more preferably 15-40N/m to the wetability of recording medium and the formation of drop particle.

Consider jetting stability similarly, the viscosity of recording liquid is preferably 1.0-30mPas, and more preferably 5.0-10.0mPas.

Consider the corrosion protection of the metal parts of contact liq in addition, the pH of recording liquid is preferably 3-11, and more preferably 6-10.

In addition, anticorrisive agent or bactericide can be included in the recording liquid, and the growth of bacterium can be inhibited and its storage stability and stable image quality can be improved like this.As anticorrisive agent and bactericide, for example can use BTA, dehydro sodium acetate, sodium sorbate, 2-pyridinethiol-1-oxide, isothiazoline based compound, Sodium Benzoate, and penta sodium pentachlorophenate.

In addition, rust inhibitor can be included in the recording liquid, can form coating on the first-class metal surface of the record of contact liq like this, to prevent its corrosion.As rust inhibitor, for example can use acid sulphite, sodium thiosulfate, sulfo-diglycolic acid ammonium, diisopropyl ammonium nilrite, pentaerythritol tetranitrate, and dicyclohexyl ammonium nitrite.

In addition, antioxidant can be included in the recording liquid, but even the antioxidant cancellation can cause the free radical material of corrosion and prevent corrosion when producing the free radical material like this.

As antioxidant, phenolic compound and amines are representational.As phenolic compound, can provide, for example, compound such as hydroquinones and gallate; With hindered phenol compound as 2,6-di-t-butyl-paracresol, β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, 2,2 '-methylene two (4-methyl-6-tert butyl phenol), 2,2 '-methylene two (4-ethyl-6-tert-butyl phenol), 4,4 '-sulfo-two (3 methy 6 tert butyl phenol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethyl-2,4,6-three (3,5-two-uncle-4-hydroxybenzyl) benzene, three (3,5-two-tertiary butyl-4-hydroxy benzyl) isocyanuric acid ester, with four [methylene-3-(3 ', 5 '-two-tert-butyl-hydroxy phenyl) propionic ester] methane.As amines, can provide, for example, N, N '-diphenyl-p-phenylenediamine (PPD), PBNA, PA, N, N '-betanaphthyl-p-phenylenediamine (PPD), N, N '-diphenyl ethylene diamine, phenthazine, N, N '-two-sec-butyl-p-phenylenediamine (PPD) and 4,4 '-tetramethyl-diaminodiphenyl-methane.In addition, for the latter, the compound of sulfur-bearing and phosphorous compound are representational.As the compound of sulfur-bearing, can provide, for example, thiodipropionate dilauryl, thio-2 acid distearyl ester, thio-2 acid lauryl stearyl, thio-2 acid two nutmeg base esters, β, β '-sulfo-two butyric acid distearyl ester, 2-mercaptobenzimidazole and dilauryl thioethers.As phosphorous compound, can provide, for example, triphenyl phosphite, tricresyl phosphite (octadecyl) ester, phosphorous acid tridecyl ester, three sulfo-tricresyl phosphite Lauryl Ester, phosphorous acid diphenyl isodecyl ester, Wytox 312 and distearyl pentaerythritol phosphite.

PH conditioning agent as being included in the recording liquid for example can use, alkali-metal hydroxide such as lithium hydroxide, NaOH, and potassium hydroxide; Ammonium hydroxide; Quaternary ammonium hydroxide; Quaternary phosphonium hydroxide; Alkali-metal carbonate such as lithium carbonate, sodium carbonate, and potash; Amine such as diethanol amine and triethanolamine; Boric acid; Hydrochloric acid; Nitric acid; Sulfuric acid; And acetate.

As ultra-violet absorber, can provide, for example, benzophenone base ultra-violet absorber, BTA base ultra-violet absorber, salicylate type ultra-violet absorber, cyanoacrylate type ultra-violet absorber and nickel complex base ultra-violet absorber.

As benzophenone base ultra-violet absorber, can provide, for example, UV-531,2-hydroxyl-4-positive 12-alkoxy benzophenone, 2,4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, with 2,2 ', 4,4 '-tetrahydroxybenzophenone.

As BTA base ultra-violet absorber, can provide, for example, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) BTA, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) BTA, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) BTA, and 2-(2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-the 5-chlorobenzotriazole.

As salicylate type ultra-violet absorber, can provide, for example, salicylic acid phenylester, salicylic acid to tert-butyl-phenyl ester and salicylic acid to the octyl phenyl ester.

As cyanoacrylate type ultra-violet absorber, can provide, for example, 2-cyano group-3,3 '-the diphenylacrylate ethyl ester, 2-cyano group-3-methyl-3-(p-methoxyphenyl) methyl acrylate and 2-cyano group-3-methyl-3-(p-methoxyphenyl) butyl acrylate cores.

As nickel complex type ultra-violet absorber, can provide, for example, two (octyl phenyl) nickel sulfide, 2,2 '-thiobis (4-tert-octyl phenol)-n-butylamine nickel (II), 2,2 '-thiobis (4-tert-octyl phenol)-2 ethyl hexylamine nickel (II) and 2,2 '-thiobis (4-tert-octyl phenol) triethanolamine nickel (II).

Passing through according to the printing ink in the ink medium group of the present invention will be at least, water, colouring agent, and wetting agent, bleeding agent as required and surfactant and other component are as required dissolved in aqueous medium or are disperseed, and further stir as required and mix and make.Dispersion can be by using, for example, and sand mill, homogenizer, ball mill, coating oscillator, or ultrasonic disperser and realize and stir and mix the agitator of routine that can be by having stirring vane, magnetic stirrer, or high speed dispersion device and realizing.

Color of ink is not particularly limited and can suitably selects according to purposes, and can provide, for example, and yellow, magenta, cyan, and black.If wherein the printing ink group that is used in combination of at least two kinds of colors is used to carry out record, then can form multicolor image, and if the printing ink group that is used in combination of wherein all colors be used to carry out record, then can form full-colour image.

In the imaging device of so constructing, 112 1 on paper is connect a ground sends into and separately from the paper feed parts, and approx vertically and the paper of upwards sending into 112 guide and be transferred to interval between transport tape 121 and the reverse rollers 122 by guider 115.In addition, the forward position of paper 112 guides and is pressed on the transport tape 121 by forward position pressure roller 125 by transmission guider 123, and its transmission direction changes about 90 °.

Then, the alternating voltage that alternately repeats positive output and negative output is applied parts by the control circuit that do not have in the drawings to show from the AC bias voltage to be applied on the charging roller 126 and with transport tape 121 usefulness AC charging die pressing types and to charge, that is the positive and negative charge-carrying belt that on sub scanning direction (its direction of rotation), alternately has constant width.If paper 112 is admitted to and alternately filled on the transport tape 121 of positive electricity and negative electricity transmission, paper 112 will be attracted on the transport tape 121 and paper 112 transmits according to rotatablely moving of transport tape 121 on sub scanning direction by electrostatic force.

Then, record head 107 drives according to picture signal, and balladeur train 103 moves up in front and back simultaneously, and with ink droplet jet line with document image to the paper 112 that stops.After the distance of paper 112 transmission regulations, write down next bar line.Finish the signal that the feather edge of signal or expression paper 112 has arrived imaging region if receive record, the record operation is finished and paper 112 is discharged to discharge paper pallet 154.

Under the situation of printed on both sides, if positive (first printing surface) record is finished, recording paper 112 is sent into two-sided paper feed unit 155 by the transport tape 121 of reverse rotation, and interval between reverse rollers 122 and the transport tape 121 is also sent in paper 112 counter-rotating (making its back side become the face that will print) once more.Similar to the above it transmitted on transport tape 121 and write down overleaf by timing controlled after, its is discharged is discharging on the paper pallet 154.

In addition, in waiting (record) to be printed process, balladeur train 103 moves to maintenance and that side of recovery mechanism 155 and the nozzle face of record head 107 and covers with cap 157, and nozzle remains on wetting state and prevents and failed by the injection that printing ink caused of drying like this.In addition, when record head 107 usefulness caps 157 covered, recording liquid sucked (being called " nozzle suction " or " head suction ") and carries out recovery operation to eliminate the recording liquid or the bubble of thickening by nozzle.Then, by using wiper scraper 158 to carry out wiping to wipe or to remove the printing ink that in the recovery operation process, adheres to the nozzle face of record head 107.In addition, before record or in the process, carry out blank spraying to spray and the irrelevant printing ink of record.Like this, hold the record a stable jet performance of 107.

Therefore, at the imaging device that comprises the equipment that is used for liquid droplets,, therefore can form high quality graphic because comprise the record head of forming by jet head according to the present invention.

At this, if used recording liquid be wherein dyestuff as the printing ink that contains dyestuff of coloured material, it is often higher with the temperature that forms ink-resistant (ink-resistant) liquid contact membranes to be used for heat treatment, but because comprise thallium, the assembly that therefore is difficult to take place thermal contraction that heat treatment causes and record head can its good dimensional accuracy and form.In addition, therein under the situation of pigment as the printing ink that contains pigment of colouring agent, often be lower than the situation of wherein using the printing ink that contains dyestuff because be used for heat treatment with the temperature that forms ink-resistant liquid contact membranes, so the thermal contraction that heat treatment caused is difficult to more to take place and the assembly of record head can its good dimensional accuracy and form.

In addition, if printing ink comprises the pigment that scribbles resin, because need not to be used to form the Technology for Heating Processing of ink-resistant liquid contact membranes, the element that thermal contraction and record head therefore do not take place can its good dimensional accuracy and form.In addition, if BTA is comprised in the printing ink as rust inhibitor, be used for that heat treatment can descend with the temperature that forms ink-resistant liquid contact membranes and the assembly of record head can its good dimensional accuracy and form.

Then, as jet head, the example of pattern of fever head is described with reference to Figure 10, this is a kind of side inkjet type head, direction and this jet head that its drop injection direction is different from the flow channel (fluid chamber) of recording liquid are similar to the jet head of previous embodiments, are electricity-thermal transition device but be used for produce power with the equipment (driving element) of liquid droplets.

Jet head constitutes like this: the flow channel that will constitute flow channel 513 sidewalls forms element 515 and is stacked on and has the base material 512 that sprays power generator 511 (wherein omitted and be used for that injection signal is applied to the electrode on the generator and be provided at protective layer on the generator as required) and go up and the nozzle plate 516 of formation nozzle 514 it on is stacked on flow channel formation element 515.In this head, printing ink flows to the central shaft of the direction of injection energy parts perpendicular to the opening of nozzle 514 in flow channel 513, shown in dotted line 517.

Have the jet head of this configuration by employing, the energy that injection power generator 511 is produced can more effectively change into the kinetic energy that is used to form ink droplet and makes its motion.In addition, have the structural advantages of recovering the printing ink meniscus by supplying with printing ink at a high speed, this is effective especially when heating element is used to spray power generator.In addition, side inkjet type jet head can be avoided so-called air pocket (cavitation) phenomenon, and this phenomenon makes that spraying power generator is destroyed gradually by the vibrations that caused of vanishing of bubble, and this is the problem in the edge ink-jet.That is, in side inkjet type jet head, if bubble development and bubble arrive nozzle, then bubble is communicated with atmosphere and temperature decline does not cause the contraction of bubble, like this life time of record head can be relative must be long.

Even in jet head that does not have oscillating plate such as above-mentioned jet head, embrittlement in the Technology for Heating Processing and thermal contraction can be by applying the present invention to nozzle plate, and flow passage plate etc. and reducing obtain having high-precision jet head like this.

In addition, although previous embodiments of the present invention is described according to the example of the imaging device that applies the present invention to be configured to printer, but the invention is not restricted to this embodiment and also can be applicable to, for example, another imaging device such as printer/facsimile machine/duplicator multi-function processor.In addition, the present invention can be applicable to use, for example, and the imaging device of another recording liquid (liquid except that printing ink or photographic fixing treat liquid).

Below describe according to recording method of the present invention.In recording method according to the present invention, as in the above-mentioned imaging device, by going up document image at recording medium (paper) from jet head liquid droplets according to the present invention.

Nozzle plate according to jet head of the present invention is at first described, the relation between recording liquid (at this, printing ink) and the recording medium (being called medium) now.As mentioned above, hydrophobicity and ink repellent (ink repellency) according to the nozzle plate of jet head of the present invention has excellence therefore, can form ink droplet (particle) well, even use is the printing ink with low surface tension.This be because nozzle plate not by too wetting and normally form the meniscus of printing ink.Owing to normally form meniscus, prevent that printing ink is drawn towards a side when ink jet, therefore, the image that can reduce the crooked of printing ink logistics and can obtain having high dot positions precision.

If print having on the low absorbefacient paper (medium), the degree of the positional precision of ink dot obviously influences picture quality.That is, because printing ink is sprawled having on the low absorbefacient paper unsmoothly, therefore form the zone of not filling printing ink, that is, blank parts is even the positional precision of ink dot only descends a little.The erratic behavior or the decline of image density is caused in this zone of not filling printing ink, causes the picture quality variation.

But in nozzle plate according to jet head of the present invention, because the positional precision height of ink dot (even using printing ink) with low surface tension, printing ink can be filled in the paper (having low absorbefacient paper even use), does not cause the erratic behavior of image density or decline like this and can obtain having the printing of high image quality.

The recording medium (medium that is used to write down) that is used for according to recording method of the present invention is below described.

Recording medium comprises support and at least one lip-deep coating of support with further comprise another layer as required.

As the medium that is used to write down, be 2-40ml/m as the amount (described amount is measured by the dynamic scan absorptiometer) that recording liquid is transferred to the printing ink on the medium that is used to write down time of contact during 100ms ², and more preferably 3-30ml/m ²Similarly, the amount (described amount is measured by the dynamic scan absorptiometer) that is transferred to the pure water of the medium that is used to write down time of contact during 100ms is preferably 2-45ml/m ², and more preferably 3-30ml/m ²About the medium that is used to write down, if the amount of pure printing ink that is shifted during 100ms time of contact or water is too little, can become pearl easily, and if too big, the diameter of record ink dot can be too less than required diameter.

In addition, as the medium that is used to write down, the amount (described amount is measured by the dynamic scan absorptiometer) that be transferred to the printing ink of the medium that is used to write down time of contact during 400ms is 3-50ml/m ², and more preferably 4-40ml/m ²Similarly, the amount (described amount is measured by the dynamic scan absorptiometer) that is transferred to the pure water of the medium that is used to write down time of contact during 400ms is preferably 3-50ml/m ², and more preferably 4-40ml/m ²About the medium that is used to write down, if time of contact, the transfer amount during 400ms was too little, its drying property may be not enough and may produces trouble trace (spur mark), and if too big, bleeding can take place easily and the glossiness of image section after drying may descend.

At this, dynamic scan absorptiometer (DSA: Japanese TAPPI JOURNAL, 48 volumes, in May, 1994, pp.88-92, Shigenori Kuga) is a kind of device that can accurately be determined at the amount of absorbed liquid in unusual short time.The dynamic scan absorptiometer is measured in the following manner automatically: based on its meniscus moving and directly read the speed that liquid absorbs in capillary, sample is shaped to discoid, with it with the helical scanning of liquid power termination, and according to the automatic gated sweep speed of preassigned pattern so that the requisite number point of destination on the sample is measured.Be used for the liquid supply head that liquid supplies on the pattern product is connected to capillary by Teflon (registration mark) pipe, and the position of the meniscus in the capillary is detected automatically by optical pickocff.Particularly, dynamic scan absorptiometer (K350 series, D type can derive from Kyowa Co., Ltd) is used to measure the pure water that shifted or the amount of printing ink.Time of contact the transfer amount when 100ms or 400ms by will near each time of contact time of contact the transfer amount that section is measured measured value push away in carrying out and measure.Measurement is carried out under 23 degrees centigrade and 50%RH.

＜support 〉

According to the purposes of paper, multiple material can be used for base material.For example, can use paper and the main adhesive-bonded fabric of mainly making of making by timber and synthetic fibers by lumber fibre.

Paper can be made by wood pulp or recycled pulps.The example of wood pulp is bleached hardwood kraft pulp (LBKP), coniferous tree bleached kraft pulp (NBKP), NBSP, LBSP, GP, and TMP.

As the material of recycled pulps, can use listed recyclable papers in the standard quality recyclable papers at paper recirculation promotion center.For example, chemical pulp or the high yield paper pulp of being made by recyclable papers can be used as base material.These recyclable papers comprise the accounting machine paper of printer media such as non-coating, heat-sensitive paper, and impact paper; OA paper such as common paper; Coated paper such as art paper, ultralight matter coated paper, and unglazed finish; With non-coated paper such as loan, colored loan, scratch paper, letter paper, wrapping paper, fancy paper (fancypaper), middle matter paper, newsprint, wood pulp fibre paper, supermarket document, simili paper, pure white spool paper and breast carton.Above material can separately or be used in combination.

Usually, recycled pulps is made by following four steps:

(1) goes fine step, will be broken into fiber and from fiber, separate printing ink with the paper of crossing in pulper with chemicals by using mechanical force.

(2) dust removal step, by using, for example, screen cloth and cleaner and remove foreign substance (as plastics) and dust in the paper of using.

(3) deinking step is discharged the printing ink that surfactant separated by using method for floating or clean method from fiber.

(4) method for bleaching is by oxidation or reduction and bleached fiber.

If recycled pulps mixes with wood pulp, the percentage of recycled pulps is preferably 40% or lower, and the paper of gained does not curl after record like this.

As the interior filler that is used for base material, can use conventional Chinese white.For example, following material can be used as Chinese white: inorganic pigment such as winnofil, powdered whiting, kaolin, clay, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulphide, zinc carbonate, satin white, alumina silicate, diatomite, calcium silicates, magnesium silicate, synthetic silica, aluminium hydroxide, alumina, lithopone, zeolite, magnesium carbonate, or magnesium hydroxide; With organic pigment such as polyglass pigment, acrylics pigment, polyethylene, microcapsules, carbamide resin, or melamine resin.Above material can separately or be used in combination.

Internal sizing agent (sizing agent) as using when producing base material can use the neutral gum rosin that is used for neutral papermaking, alkenyl succinic anhydrides (ASA), alkyl ketene dimer (AKD), or Petropols glue.Especially, neutral gum rosin and alkenyl succinic anhydrides are preferred.Alkyl ketene dimer has high glue blending function, therefore just can provide enough glue blending functions when use is a small amount of.But because alkyl ketene dimer reduces the skin-friction coefficient of record-paper (medium), the record-paper that uses alkyl ketene dimer to make causes slip in the time of may transmitting in ink-jet recording apparatus.

＜coating 〉

Coating comprises pigment and adhesive, and also can comprise surfactant and other component.

As pigment, can use the mixture of inorganic pigment or inorganic pigment and organic pigment.

For example, kaolin, talcum, powdered whiting, winnofil, calcium sulfite, amorphous silica, alumina, titanium white, magnesium carbonate, titanium dioxide, aluminium hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, or chlorite can be used as inorganic pigment.Especially, kaolin provides the high-gloss surface that is similar to gelatine printing paper and is preferred therefore.

The kaolin that several types is arranged, for example, layering kaolin, calcined kaolin and the engineering kaolin of making by surface modification.For high-gloss surface is provided, wherein the mass percent of the sort of kaolin in the kaolin total amount with 2 μ m or lower diameter of 80 quality % or more particles is preferably 50% or more.

Adhesive and the kaolin mass ratio in coating is preferably 100: 50.If kaolinic mass ratio is lower than 50, can not obtain enough glossiness.Kaolinic amount is not particularly limited.If but considered kaolin flowability and thickening properties under high shear, kaolinic mass ratio would be preferably 90 or lower (but with regard to coating).

As organic pigment, for example can use styrene-propene acid copolymer particle, SB particle, granules of polystyrene, or the water-soluble dispersion of polyethylene particle.Above organic pigment can be used in combination.

The amount of organic pigment in the coating color total amount is preferably 2-20 quality %.The proportion of aforesaid organic pigment is lower than the proportion of inorganic pigment, but therefore provides the thick high gloss coating with good coating.If the mass percent of organic pigment is lower than 2%, can not obtain required effect.If the mass percent of organic pigment surpasses 20%, it is too low that the flowability of applying liquid becomes, the result, and the decrease in efficiency of coating processes and running cost increase.

Organic pigment can be divided into several types according to its grain shape: solid shape, hollow shape, and ring shape.In order to realize glossiness, but coating, and well balanced between the flowability of applying liquid, the organic pigment with hollow shape particle of space percentage 40% or higher and average diameter 0.2 to 3.0 μ m is preferred.

As adhesive, preferably use water-based resin.

As water-based resin, can use water-soluble resin or water-dispersed resin.Can use the water-based resin of any kind according to purposes.For example, can use following water-based resin: polyvinyl alcohol; Modified polyethylene alcohol as anion-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, or acetal modified polyethylene alcohol; Polyurethane; PVP; Modified polyethylene base pyrrolidones such as PVP-vinyl acetate copolymer, vinyl pyrrolidone-dimethylaminoethyl acrylate methyl base amino-ethyl ester copolymer, quaternised vinyl pyrrolidone-dimethylaminoethyl acrylate methyl base amino-ethyl ester copolymer, or vinyl pyrrolidone-Methacrylamide oxypropyl trimethyl ammonium chloride copolymer; Cellulose such as carboxy methyl cellulose, hydroxy ethyl cellulose, or hydroxy propyl cellulose; Modified cellulose such as cationization hydroxy ethyl cellulose; Polyester, polyacrylic acid (ester), melamine resin, or the modified form of these materials; The synthetic resin of making by the polyester-polyurethane ester copolymer; With other material as poly-(methyl) acrylic acid, poly-(methyl) acrylamide, oxidized starch, phosphorylated starch, from converted starch, cationic starch, the starch of other modification, PEO, Sodium Polyacrylate, and mosanom.Above material can separately or be used in combination.

In above material, polyvinyl alcohol, cation-modified polyvinyl alcohol, acetal modified polyethylene alcohol, polyester, polyurethane and polyester-polyurethane ester copolymer are being especially preferred aspect the absorption of inks speed.

Can use the water-dispersed resin of any kind according to purposes.For example, can use following water-dispersed resin: polyvinyl acetate, ethene-polyvinyl acetate ester copolymer, polystyrene, styrene-(methyl) acrylate copolymer, (methyl) acrylate polymer, polyvinyl acetate-(methyl) acrylic acid (ester) copolymer, SB, ethylene-propylene copolymer, polyvingl ether and silicone-acrylic analog copolymer.Water-dispersed resin can comprise crosslinking agent such as methylol melamine, methylol hydroxy propylidene urea, or isocyanates.In addition, the self-crosslinking copolymer that comprises the NMA unit can be used as water-dispersed resin.Two or more above-mentioned water-dispersed resins can use simultaneously.

The water-based resin in the coating and the mass ratio of pigment are preferably 2: 100 to 100: 100, and more preferably 3: 100 to 50: 100.The amount of water-based resin in coating is defined as making that the liquid absorption of recording medium falls in the scope of regulation.

If use the colouring agent of water dispersible, the mixed-cation organic compound can be selected in adhesive.For example, can use with water-based ink in direct dyes or the sulfonic acid group of acid dyes, carboxylic group, or amino group reaction, and the uncle who forms insoluble salt is to tertiary amine; Or the monomer of quaternary ammonium salt, oligomer, or polymer.Wherein, the oligomer of quaternary ammonium salt and polymer are especially preferred.

As the cation organic compound, can use following material: dimethylamine-chloropropylene oxide condensation polymer, dimethylamine-ammonia-chloropropylene oxide condensation product, poly-(trimethyl amino-ethyl-methacrylate Methylsulfate), diallyl amine hydrochlorate-acrylamide copolymer, poly-(diallyl amine hydrochlorate-sulfur dioxide), the PAH hydrochloride, poly-(allylamine hydrochloride-diallyl amine hydrochlorate), acrylamide-diallylamine copolymer, the polyvinylamine copolymer, dicyandiamide, dicyandiamide-ammonium chloride-melocol condensation product, polyalkylene polyamine-dicyandiamide ammonium salt condensation product, dimethyl diallyl ammonium chloride, poly-(diallyl methylamine) hydrochloride, poly-(diallyldimethylammonium chloride), poly-(diallyldimethylammonium chloride-sulfur dioxide), poly-(diallyldimethylammonium chloride-diallyl amine hydrochlorate derivative), acrylamide-diallyldimethylammonium chloride copolymer, acrylate-acrylamide-diallyl amine hydrochlorate copolymer, polymine, aziridine derivative such as acrylic amine polymer and modified polyethylene imines oxyalkylene.Above material can separately or be used in combination.

Preferred combination uses the cation organic compound that has low-molecular-weight cation organic compound such as dimethylamine-chloropropylene oxide condensation polymer or PAH hydrochloride and have higher molecular weight as poly-(diallyldimethylammonium chloride).Compare with wherein only using a kind of situation of cation organic compound, being used in combination of multiple cation organic compound improves image density and reduces emergence.

The equivalent weight of cation in the cation organic compound that obtains by colloidal titration method (using polyvinyl potassium sulfate and toluidine blue to carry out) is preferably 3 to 8meq/g.If equivalent weight is in above scope, the dry deposition quality of cation organic compound falls in the preferred range.When measuring cationic equivalent weight, make the solids content in the solution become 0.1 quality % with distillating the water dilution cation organic compound.Do not carry out pH control.

The dry deposition quality optimization of cation organic compound is 0.3 to 2.0g/m ²If the dry deposition quality of cation organic compound is lower than 0.3g/m ², possibly can't realize the abundant raising of image density and the abundant minimizing of emergence.

Can use any surfactant according to purposes.For example, can use anion surfactant, cationic surfactant, amphoteric surfactant, or non-ionic surface active agent.In above surfactant, non-ionic surface active agent is especially preferred.The adding of surfactant improves the resistance to water and the density of image, thereby reduces bleeding.

For example, can use following non-ionic surface active agent: the higher alcohol ethylene oxide adduct, the alkylphenol ethylene oxide adduct, fatty acid oxidation ethene addition product, the polyol fatty acid ester ethylene oxide adduct, higher aliphatic amine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, fat oil ethylene oxide adduct, the ethylene oxide adduct of fat, the polypropylene glycol ethylene oxide adduct, fatty acid glyceride, pentaerythritol fatty ester, sorbierite-fatty acid esters of sorbitan, sucrose fatty ester, polyol alkyl ether and alkanolamine fatty acid amide.Above material can separately or be used in combination.

Polyalcohol is not limited to particular types and can uses the polyalcohol of any kind of according to purposes.For example, can use glycerine, trimethylolpropane, pentaerythrite, sorbierite, or sucrose.Ethylene oxide adduct can be replaced a part of ethylene oxide and make with oxyalkylene such as propylene oxide or butylene oxide not influence water miscible degree.The percentage of replacing part is preferably 50% or lower.The hydrophil lipophil balance of non-ionic surface active agent (HLB) is preferably 4 to 15, and more preferably 7 to 13.

The mass ratio of surfactant and cation organic compound is preferably 0: 100 to 10: 100, and more preferably 0.1: 100 to 1: 100.

Other component also can add in the coating, as long as its favourable effect is without prejudice.The example of other component comprises additive such as alumina powder, pH conditioning agent, anticorrisive agent, and antioxidant.

The method that forms coating is not limited to ad hoc approach.For example, coating can be by forming base material with the applying liquid dipping or by applying liquid is applied on the base material.For the dipping or the coating of applying liquid, can use spreader such as conventional sizing applicator (size press), door roller sizing applicator, film shifts sizing applicator, Scraper applicator, bar spreader, airblade coating device, or curtain coating device.In addition, use the conventional sizing applicator that invests on the paper machine, door roller sizing applicator, or film transfer sizing applicator is used for the dipping of applying liquid or is coated with improving process efficiency.

Amount to the applying liquid on the base material is not particularly limited.But the solids content of the applying liquid on the base material is preferably 0.5 to 20g/m ², and more preferably 1 to 15g/m ²After the dipping or coating of applying liquid, applying liquid can be dried.The temperature of this drying process is preferably 100 to 250 degrees centigrade, but is not limited to particular range.

The exemplary record medium that is used for recording method of the present invention also can have backing layer on the back side of base material, and other layer between base material and the coating or between base material and the backing layer.In addition, protective layer can be set on coating.Each layer can be made up of one or more layers.

If being absorbed in the above scope of the present invention of liquid, the recording medium that is used for recording method of the present invention can also be the commercially available coated paper that is used for offset printing except ink-jet recording medium, is used for the coated paper of intaglio plate.

Preferably, the gram number that is used for the recording medium of recording method of the present invention is 50 to 250g/m ²If it is lower than 50g/m ², be easy to generate bad transmission: recording medium is blocked on the transmission distance and makes there is not intensity.If the gram number of recording medium surpasses 250g/m ², recording medium can not be finished the rotation on bending part in transmission course, make the intensity of paper become too strong, is easy to generate bad transmission like this, causes recording medium to stop up.

Specific practical embodiments is below described.But the invention is not restricted to these practical embodiments.

(preparation embodiment 1)

-preparation comprise copper phthalocyanine polymer fine particles dispersion-

In order to prepare the dispersion of the polymer fine particles that comprises copper phthalocyanine, will have mechanical agitator, thermometer, nitrogen inlet tube, the air in the 1L flask of return duct and dropping funel is fully replaced with nitrogen; The 11.2g styrene of packing in the 1L flask, 2.8g acrylic acid, 12.0g methacrylic acid Lauryl Ester, 4.0g polyethylene glycol methacrylate-styrene polymer, 4.0g styrene macromonomer (Toagosei Co., Ltd, trade (brand) name: AS-6) and the 0.4g mercaptoethanol; And temperature is risen to 65 degrees centigrade.Then, with 100.8g styrene, 25.2g acrylic acid, 108.0g methacrylic acid Lauryl Ester, 36.0g polyethylene glycol methacrylate-styrene polymer, 60.0g methacrylic acid hydroxyethyl ester, 36.0g the styrene macromonomer (Toagosei Co., Ltd, trade (brand) name: AS-6), the 3.6g mercaptoethanol, 2.4g the mixed solution of two methyl pentane nitriles of azo and 18.0g methyl ethyl ketone splashed into this 1L flask in 2.5 hours.

After being added dropwise to complete, the mixed solution of two methyl pentane nitriles of 0.8g azo and 18.0g methyl ethyl ketone was splashed into the 1L flask in 0.5 hour.Gained solution adds this solution 65 degrees centigrade of following slakings of temperature 1 hour with the two methyl pentane nitriles of 0.8g azo, and subsequently with the further slaking of this solution 1 hour.After reaction stops, the 364g methyl ethyl ketone is added the 1L flask.As a result, obtain the polymer solution that 800g has concentration 50 quality %.A part of resulting polymers solution is dry also by gel permeation chromatography (standard: polystyrene, solvent: oxolane) measure its weight average molecular weight (Mw).Weight average molecular weight is 15,000.

Then, with 28g resulting polymers solution, the 26g copper phthalocyanine, 13.6g 1mol/L potassium hydroxide solution, 20g methyl ethyl ketone and 30g ion exchange water mix and fully stir.The gained material is used three utmost point roller mills (Noritake Co., Limited, trade (brand) name: NR-84A) mediate 20 times.The gained pastel is put into 200g ion exchange water and stirring.Methyl ethyl ketone in the liquid and water distill by using evaporimeter.As a result, obtain the polymer fine particles dispersion that 160g has the cyan color.Solids content in this polymer fine particles dispersion is 20.0 quality %.

The average particulate diameter of the polymer fine particles in the polymer fine particles dispersion (D50%) uses size distribution analyser (Microtrac UPA, Nikkiso Co., Ltd) to measure.Average particulate diameter is 93nm.

(preparation embodiment 2)

-preparation comprise dimethylquinacridone pigment polymer fine particles dispersion-

Polymer fine particles dispersion with magenta color goes up substantially according to the mode identical with preparation embodiment 1 and prepares, except with C.I. pigment red 122 instead of copper phthalocyanine color.

The average particulate diameter of the polymer fine particles in the polymer fine particles dispersion (D50%) uses size distribution analyser (Microtrac UPA, Nikkiso Co., Ltd) to measure.Average particulate diameter is 127nm.

(preparation embodiment 3)

-preparation comprise monoazo yellow pigment polymer fine particles dispersion-

Polymer fine particles dispersion with yellow color goes up substantially according to the mode identical with preparation embodiment 1 and prepares, except with C.I. pigment yellow 74 instead of copper phthalocyanine colors.

The average particulate diameter of the polymer fine particles in the polymer fine particles dispersion (D50%) uses size distribution analyser (Microtrac UPA, Nikkiso Co., Ltd) to measure.Average particulate diameter is 76nm.

(preparation embodiment 4)

The dispersion of the carbon black that-preparation is handled with sulfonating agent-

In order to prepare carbon black dispersion, (Printex#85 Degussa) sneaks into the 400ml sulfolane with the commercially available charcoal blacks of 150g; Solution is loose with the ball mill differential; The 15g amidosulphuric acid is added this solution; And subsequently solution was stirred 10 hours down at 140-150 degree centigrade.The gained slurry is put into the 1000ml ion exchange water, and with this solution 12, centrifugal under the 000rpm.As a result, obtain surface-treated carbon black wet cake.Gained carbon black wet cake is dispersed in 2 once more, in the 000ml ion exchange water; The pH of solution regulates with lithium hydroxide; Solution use ultrafilter desalination/concentrate; And subsequently solution is filtered with the nylon filter with average pore size 1 μ m.As a result, obtain having the black carbon black dispersion of pigment concentration 10 quality %.

Fine grain average particulate diameter (D50%) in the carbon black dispersion uses size distribution analyser (Microtrac UPA, Nikkiso Co., Ltd) to measure.Average particulate diameter is 80nm.

(production example 1)

-production cyan ink-

In order to produce cyan ink, dispersion with 20.0 quality % polymer fine particles that comprises copper phthalocyanine of preparation in preparation embodiment 1,23.0 quality %3-methyl isophthalic acid, the 3-butanediol, 8.0 quality % glycerine, 2.0 quality %2-ethyl-1, the 3-hexylene glycol, 2.5 quality % is as the FS-300 (DuPont) of fluorinated surfactant, 0.2 quality % is as the Proxel LV (Avecia KK) of anticorrisive agent or bactericide, 0.5 quality %2-amino-2-ethyl-1, ammediol and a certain amount of ion exchange water mix (amounting to 100 quality %); And use film filter to filter the mixture with average pore size 0.8 μ m.

(production example 2)

-production magenta ink-

In order to produce magenta ink, dispersion with 20.0 quality % polymer fine particles that comprises dimethylquinacridone pigment of preparation in preparation embodiment 2,22.5 quality %3-methyl isophthalic acid, the 3-butanediol, 9.0 quality % glycerine, 2.0 quality %2-ethyl-1, the 3-hexylene glycol, 2.5 quality % is as the FS-300 (DuPont) of fluorinated surfactant, 0.2 quality % is as the Proxel LV (AveciaKK) of anticorrisive agent or bactericide, 0.5 quality %2-amino-2-ethyl-1, ammediol and a certain amount of ion exchange water mix (amounting to 100 quality %); And use film filter to filter the mixture with average pore size 0.8 μ m.

(production example 3)

-production Yellow ink-

In order to produce Yellow ink, dispersion with 20.0 quality % polymer fine particles that comprises monoazo yellow pigment of preparation in preparation embodiment 3,24.5 quality %3-methyl isophthalic acid, the 3-butanediol, 8 quality % glycerine, 2.0 quality %2-ethyl-1, the 3-hexylene glycol, 2.5 quality % is as the FS-300 (DuPont) of fluorinated surfactant, 0.2 quality % is as the Proxel LV (Avecia KK) of anticorrisive agent or bactericide, 0.5 quality %2-amino-2-methyl-1, ammediol and a certain amount of ion exchange water mix (amounting to 100 quality %); And use film filter to filter the mixture with average pore size 0.8 μ m.

(production example 4)

-production black ink-

In order to produce black ink, carbon black dispersion with 20.0 quality % preparation in preparation embodiment 4,22.5 quality %3-methyl isophthalic acid, the 3-butanediol, 7.5 quality % glycerine, 2.0 quality %2-pyrrolidones, 2.0 quality %2-ethyl-1, the 3-hexylene glycol, 2.5 quality % is as the FS-300 (DuPont) of fluorinated surfactant, 0.2 quality % is as the Proxel LV (Avecia KK) of anticorrisive agent or bactericide, 0.5 quality %2-amino-2-methyl-1, ammediol and a certain amount of ion exchange water mix (amounting to 100 quality %); And use film filter to filter the mixture with average pore size 0.8 μ m.

The surface tension of the printing ink of in production example 1 to 4, making and viscosity mensuration as described below.The result provides in following table 2.

＜measurement viscosity 〉

Ink viscosity 25 degrees centigrade of R-500 viscosimeters that use down Toki Sangyo Co., Ltds (1 ° 34 of cone angle ' * R24,60rpm is after 3 minutes) measure.

＜surface tension 〉

The static surface tension of printing ink uses the surface tensiometer (CBVP-Z of Kyowa interface science Co., Ltd) that adopts the platinum plate to measure down at 25 degrees centigrade.

Table 2

	Viscosity (mPas)	Surface tension (mN/m)
	Viscosity (mPas)	Surface tension (mN/m)	Production example 1	8.05	25.4
Production example 2	8.09	25.4	Production example 1	8.05	25.4
Production example 2	8.09	25.4	Production example 3	8.11	25.7
Production example 4	8.24	25.4	Production example 3	8.11	25.7

-production base material-

Has gram number 79g/m ²The base material 0.3 quality % slurry manufacturing of using fourdrinier machine to make by the material in the following prescription.In the size press step of paper technology, with the oxidized starch solution coat to base material.The solids content of the oxidized starch on the base material is 1.0g/m ²

Broad-leaved bleached kraft pulp (LBKP) 80 quality %

Needle bleached kraft pulp (NBKP) 20 quality %

Winnofil (trade (brand) name: TP-121, Okutama Kogyo Co., Ltd) 10 quality %

Aluminum sulfate 1.0 quality %

Amphoteric starch (trade (brand) name: Cato3210, Nippon NSC Ltd.) 1.0 quality %

Neutral gum rosin (trade (brand) name: NeuSize M-10, Harima Chemicals, Inc.) 0.3 quality %

Retention agent (trade (brand) name: NR-11LS, HYMO Co., Ltd) 0.02 quality %

(production example 1)

-record of production medium 1-

Applying liquid with solids content concn 60 quality % is by mixing the clay (in described clay, the particle of 97 quality %s have diameter 2 μ ms or lower) of 70 quality % as pigment; 30 quality % have the powdered whiting of average particulate diameter 1.1 μ m; 8 quality % SB emulsions (as adhesive, have glass transformation temperature (Tg)-5 degree centigrade); 1 quality % organic phosphate starch; 0.5 quality % is as the calcium stearate of auxiliary agent; Make with water.

For record of production medium 1, the gained applying liquid is used Scraper applicator to be applied to make on the two sides of above base material 8g/m ²The applying liquid of solids content adheres to every; And base material is by the hot-air drying and carry out supercalendering.

(production example 2)

-record of production medium 2-

Applying liquid with solids content concn 60 quality % is by mixing the clay (in described clay, the particle of 97 quality %s have diameter 2 μ ms or lower) of 70 quality % as pigment; 30 quality % have the powdered whiting of average particulate diameter 1.1 μ m; 7 quality % SB emulsions (as adhesive, have glass transformation temperature (Tg)-5 degree centigrade); 0.7 quality % organic phosphate starch; 0.5 quality % is as the calcium stearate of auxiliary agent; Make with water.

For record of production medium 2, the gained applying liquid is used Scraper applicator to be applied to make on the two sides of above base material 8g/m ²The applying liquid of solids content adheres to every; And base material is dry and carry out supercalendering by hot-air.

(first embodiment)

-printing ink group, recording medium and image record-

By conventional method, prepare the cyan ink of making by in production example 1, the magenta ink of in production example 2, making, the printing ink group 1 that Yellow ink of making and the black ink of making are formed in production example 3 in production example 4.

Using printing ink group 1 (maximum ink drop size: 18pl) print image using the 300dpi drop to have on the required printer prototype plant that nozzle resolution ratio is nozzle 384, embodiment of the present invention under the image resolution ratio 600dpi on the recording medium 1.The total ink of the per unit area of secondary colour is restricted to 140% and form colored (solid-color) image and character on the spot.

(second embodiment)

-printing ink group, recording medium and image record-

Image forms according to the mode identical with first embodiment basically, except recording medium 2 is used as recording medium.

(the 3rd embodiment)

-printing ink group, recording medium and image record-

Image forms according to the mode identical with first embodiment basically, and (trade (brand) name: Space DX restrains number=56g/m to the commercially available coated paper of using except intaglio printing ², Nippon Paper Co., Ltd) and (below be called recording medium 3) as recording medium.For each recording medium 1, recording medium 2, recording medium 3 uses the dynamic scan absorptiometer to measure the transfer amount of the cyan ink of producing in the transfer amount of pure water and the production example 1 in accordance with the following methods.The results are shown in table 3.

The pure water that the measurement of＜use dynamic scan absorptiometer is shifted and the amount of cyan ink 〉

For each above recording medium, the pure water that is shifted and the amount of cyan ink use dynamic scan absorptiometer (K350 series, D type, Kyowa Co., Ltd) to measure under 25 degrees centigrade and 50%RH.

The pure water that is shifted under 100ms and the 400ms in time of contact and the amount of cyan ink obtain by pushing away in the transfer amount of using near the time point determining each time of contact.

Table 3

		Pure water		The printing ink of production example 1 (γ=25)
		Pure water		The printing ink of production example 1 (γ=25)		Time of contact: 100ms	Time of contact: 400ms	Time of contact: 100ms	Time of contact: 400ms
		First embodiment	Recording medium 1	10.1ml/m ²	20.2ml/m ²	Time of contact: 100ms	Time of contact: 400ms	Time of contact: 100ms	Time of contact: 400ms	7.2ml/m ²	14.8ml/m ²
Second embodiment	Recording medium 2	First embodiment	Recording medium 1	10.1ml/m ²	20.2ml/m ²	25.2ml/m ²	28.5ml/m ²	14.6ml/m ²	19.4ml/m ²	7.2ml/m ²	14.8ml/m ²
Second embodiment	Recording medium 2	The 3rd embodiment	Recording medium 3	10.4ml/m ²	21.8ml/m ²	25.2ml/m ²	28.5ml/m ²	14.6ml/m ²	19.4ml/m ²	6.4ml/m ²	8.8ml/m ²

Aspect Cheng Zhu, bleeding, trouble trace and glossiness, be evaluated at the quality of the image that prints in first to the 3rd embodiment.The results are shown in table 4.

＜Cheng Zhu 〉

The green of the printing Cheng Zhudu of coloured image is on the spot assessed by perusal according to following evaluation criteria.

[evaluation criteria]

AA: do not observe into pearl and image evenly prints.

BB: observe into pearl a little.

CC: obviously observe into pearl.

DD: observe excessive Cheng Zhu.

＜bleeding 〉

The Bleeding of black character in yellow background of printing assessed by perusal according to following evaluation criteria.

[evaluation criteria]

AA: do not observe bleeding and print character clearly.

BB: observe bleeding a little.

CC: obviously observe bleeding.

DD: it is fuzzy to observe excessive bleeding and character outline.

＜trouble trace 〉

The degree of the trouble trace in the printing image is assessed by perusal according to following evaluation criteria.

[evaluation criteria]

AA: do not observe the trouble trace.

BB: observe the trouble trace a little.

CC: obviously observe the trouble trace.

DD: observe excessive trouble trace.

＜glossiness 〉

The glossiness of printing image is assessed by perusal according to following evaluation criteria.

[evaluation criteria]

AA: image has press polish.

BB: image is glossy.

CC: image is lackluster.

Table 4

	Cheng Zhu	Bleeding	The trouble trace	Glossiness
	Cheng Zhu	Bleeding	The trouble trace	Glossiness	First embodiment	BB	BB	BB	BB
Second embodiment	AA	AA	AA	BB	First embodiment	BB	BB	BB	BB
Second embodiment	AA	AA	AA	BB	The 3rd embodiment	BB	BB	BB	AA

[appendix]

Below provide typical embodiment of the present invention (1) to (40).

Embodiment (1) is a jet head, the nozzle that comprises the drop that is configured to injection record liquid, be communicated to the fluid chamber on the nozzle, with be configured to the energy generation apparatus that produce power is used for the recording liquid of pressurized fluid body cavity, be characterised in that the flow channel that is configured to define the flow channel that is used for recording liquid forms that element is made by the metal material that comprises nickel and the peak intensity of (200) face of nickel is higher than the peak intensity of (111) face of nickel, described intensity is utilized the X-ray diffraction analysis and is measured.

Embodiment (2) is the jet head according to above embodiment (1), is characterised in that the metal material of making flow channel formation element comprises thallium.

Embodiment (3) is the jet head according to above embodiment (2), is characterised in that the content of thallium is not more than 1% quality.

Embodiment (4) is the jet head according to above embodiment (1), is characterised in that flow channel forms element and comprises cobalt.

Embodiment (5) is the jet head according to above embodiment (4), is characterised in that the content of cobalt is not more than 1% quality.

Embodiment (6) is the jet head according to above embodiment (1), is characterised in that flow channel forms element and comprises manganese.

Embodiment (7) is the jet head according to above embodiment (4), is characterised in that the content of manganese is not more than 1% quality.

Embodiment (8) is a jet head, the mouth of disputing that comprises the drop that is configured to injection record liquid, be communicated to the fluid chamber on the nozzle, with be configured to the energy generation apparatus that produce power is used for the recording liquid of pressurized fluid body cavity, be characterised in that the flow channel that is configured to define the flow channel that is used for recording liquid forms element and made by the metal material that comprises nickel and thallium.

Embodiment (9) is the jet head according to above embodiment (8), is characterised in that the peak intensity of (200) face of nickel is higher than the peak intensity of (111) face of nickel, and described intensity is measured by the X-ray diffraction analysis.

Embodiment (10) is the jet head according to arbitrary above embodiment (1) to (9), the volume efficiency of orientation crystal face of ratio of peak intensity that is characterised in that (111) face of the peak intensity of (200) face that is defined as nickel and nickel satisfies relations I (200)/I (111)＞1.0, wherein I (111) is the peak intensity of (111) face of nickel and the peak intensity of (200) face that I (200) is nickel, and described intensity is utilized the X-ray diffraction analysis and measured.

Embodiment (11) is the jet head according to arbitrary above embodiment (1) to (10), is characterised in that flow channel forms the content that element comprises sulphur and sulphur and is not more than 0.1% quality.

Embodiment (12) is the jet head according to arbitrary above embodiment (1) to (11), is characterised in that it is the mouth plate of disputing that is configured to define nozzle that flow channel forms element.

Embodiment (13) is the jet head according to arbitrary above embodiment (1) to (12), is characterised in that it is the flow passage plate that is configured to define fluid chamber that flow channel forms element.

Embodiment (14) is the jet head according to arbitrary above embodiment (1) to (13), is characterised in that it is the oscillating plate with the element that is configured to define the fluid chamber wall surface that flow channel forms element.

Embodiment (15) is the jet head according to arbitrary above embodiment (1) to (14), be characterised in that comprising at least two is selected from following element: the nozzle plate that is configured to define nozzle, be configured to define the flow passage plate of fluid chamber, with the oscillating plate with the element that is configured to define the fluid chamber wall surface, wherein said two elements form integral body.

Embodiment (16) is the jet head according to arbitrary above embodiment (1) to (15), is characterised in that flow channel forms element and forms by electrocasting.

Embodiment (17) is the jet head according to arbitrary above embodiment (1) to (16), is characterised in that the Vickers hardness of flow channel formation element is that 250 (Hv) are to 500 (Hv).

Embodiment (18) is the jet head according to arbitrary above embodiment (1) to (17), is characterised in that it is a side inkjet type head, and wherein the direction of liquid droplets is different from the direction of the flow channel that is used for recording liquid.

Embodiment (19) is an imaging device, comprises the record head of the drop that is configured to injection record liquid, is characterised in that record head is the jet head according to arbitrary above embodiment (1) to (18).

Embodiment (20) is the imaging device according to above embodiment (19), is characterised in that recording liquid is to comprise the printing ink of dyestuff as coloured material.

Embodiment (21) is the imaging device according to above embodiment (19), is characterised in that recording liquid is to comprise the printing ink of pigment as coloured material.

Embodiment (22) is the imaging device according to above embodiment (19), is characterised in that recording liquid is the printing ink that comprises polymer fine particles, wherein comprises the granules of pigments as coloured material.

Embodiment (23) is the imaging device according to above embodiment (19), is characterised in that recording liquid is the printing ink that comprises BTA.

Embodiment (24) is the equipment that is configured to from the jet head liquid droplets, is characterised in that the jet head that comprises according to arbitrary above embodiment (1) to (18).

Embodiment (25) is recording method, is characterised in that from drop according to the jet head injection record liquid of arbitrary above embodiment (1) to (18), thereby at the enterprising line item of recording medium.

Embodiment (26) is the recording method according to above embodiment (25), is characterised in that recording medium is the medium that is used to write down, and has support and the coating on the one side at least of support.

Embodiment (27) is the recording method according to above embodiment (25) or (26), is characterised in that the amount that is transferred to the recording liquid of recording medium time of contact during 100ms is 2-40ml/m ²And the amount that be transferred to the recording liquid of recording medium time of contact during 400ms is 3-50ml/m ², described amount is measured by dynamic scan liquid absorptiometer under 23 degrees centigrade and 50%RH.

Embodiment (28) is the recording method according to above embodiment (25) or (26), is characterised in that the amount that is transferred to the pure water of recording medium time of contact during 100ms is 2-45ml/m ²And the amount that be transferred to the pure water of recording medium time of contact during 400ms is 3-50ml/m ², described amount is measured by dynamic scan liquid absorptiometer under 23 degrees centigrade and 50%RH.

Embodiment (29) is the recording method according to above embodiment (25), is characterised in that the amount that recording medium comprises the solid adhesion in base material and coating and the coating at least is 0.5-20.0g/m ²

Embodiment (30) is the recording method according to above embodiment (25), and the weight that is characterised in that recording medium is 50-250g/m ²

Embodiment (31) is the recording method according to above embodiment (25), is characterised in that recording medium is carried out supercalendering.

Embodiment (32) is the recording method according to arbitrary above embodiment (25) to (31), is characterised in that recording medium comprises pigment and pigment is kaolin.

Embodiment (33) is the recording method according to arbitrary above embodiment (25) to (31), is characterised in that recording medium comprises pigment and pigment is powdered whiting.

Embodiment (34) is according to the recording method of arbitrary above embodiment (25) to (33), is characterised in that recording medium comprises water-base resin.

Embodiment (35) is the recording method according to above embodiment (34), is characterised in that water-base resin is water-soluble resin or water-dispersed resin.

Embodiment (36) is the recording method according to arbitrary above embodiment (25) to (35), is characterised in that recording liquid comprises water at least, colouring agent, and wetting agent.

Embodiment (37) is the recording method according to arbitrary above embodiment (25) to (36), is characterised in that the surface tension of recording liquid under 25 degrees centigrade is 15-40mN/m.

Embodiment (38) is the recording method according to arbitrary above embodiment (25) to (37), is characterised in that it is 0.01-0.16 μ m as colouring agent and average particulate diameter that should the dispersiveness colouring agent that recording liquid comprises dispersed colouring agent.

Embodiment (39) is the recording method according to arbitrary above embodiment (25) to (38), is characterised in that the viscosity of recording liquid under 25 degrees centigrade is 1-30mPasec.

Embodiment (40) is the recording method according to arbitrary above embodiment (25) to (39), is characterised in that recording liquid comprises surfactant and surfactant is a fluorine-containing surfactant.

Jet head according at least a above-mentioned typical embodiments, do not have or the little effect Technology for Heating Processing in fragility and thermal contraction and be connected precision or dimensional accuracy is improved, can obtain the jet head of better quality like this, because be configured to define that the flow channel of the flow channel that is used for recording liquid forms that element is made by the metal material that comprises nickel and the peak intensity of (200) face of nickel is higher than the peak intensity of (111) face of nickel, described intensity is utilized the X-ray diffraction analysis and is measured.

Jet head according at least a above-mentioned typical embodiments, do not have or the little effect Technology for Heating Processing in fragility and thermal contraction and be connected precision or dimensional accuracy is improved, can obtain the jet head of better quality like this, because being configured to define the flow channel formation element of the flow channel that is used for recording liquid is made by the metal material that comprises nickel and thallium, therefore, can easily obtain a kind of like this configuration, the peak intensity of (200) face of nickel is higher than the peak intensity of (111) face of nickel, and described intensity is measured by the X-ray diffraction analysis.

According to the imaging device of at least a above-mentioned typical embodiments, can form the image of better quality, because the jet head of at least a above-mentioned typical embodiment is provided.

Be configured to the equipment of liquid droplets according at least a above-mentioned typical embodiments, can obtain a kind ofly comprising the equipment better quality jet head, that be configured to liquid droplets, because the jet head of at least a above-mentioned typical embodiment is provided.

According to the recording method of at least a above-mentioned typical embodiments, can write down the image of better quality, because record is undertaken by the jet head liquid droplets from least a above-mentioned typical embodiment.

The invention is not restricted to concrete disclosed embodiment and can in the case without departing from the scope of the present invention these embodiments be changed and/or improve.

The application requires the foreign priority based on Japanese patent application No.2005-327468 (on November 11st, 2005 submitted) and Japanese patent application No.2006-025111 (on February 1st, 2006 submitted), and its whole contents is incorporated the present invention into as a reference at this.

Industrial applicibility

The present invention can be applicable to jet head, and especially, the jet head that hydrophobic is processed is carried out on its surface, and imaging device especially, has the imaging device of this jet head, is used for the equipment of liquid droplets, and recording method.

Claims

1. jet head, the nozzle that comprises the drop that is configured to injection record liquid, be communicated to the fluid chamber on the nozzle, with be configured to the energy generation apparatus that produce power is used for the recording liquid of pressurized fluid body cavity, the flow channel that wherein is configured to define the flow channel that is used for recording liquid forms that element is made by the metal material that comprises nickel and the peak intensity of (200) face of nickel is higher than the peak intensity of (111) face of nickel, and described intensity is utilized the X-ray diffraction analysis and measured.

2. according to the jet head of claim 1, the metal material of wherein making flow channel formation element comprises thallium.

3. according to the jet head of claim 2, wherein the content of thallium is not more than 1% quality.

4. according to the jet head of claim 1, wherein flow channel formation element comprises cobalt.

5. according to the jet head of claim 4, wherein the content of cobalt is not more than 1% quality.

6. according to the jet head of claim 1, wherein flow channel formation element comprises manganese.

7. according to the jet head of claim 4, wherein the content of manganese is not more than 1% quality.

8. jet head, the nozzle that comprises the drop that is configured to injection record liquid, be communicated to the fluid chamber on the nozzle, with be configured to the energy generation apparatus that produce power is used for the recording liquid of pressurized fluid body cavity, the flow channel that wherein is configured to define the flow channel that is used for recording liquid forms element and is made by the metal material that comprises nickel and thallium.

9. jet head according to Claim 8, wherein the peak intensity of (200) face of nickel is higher than the peak intensity of (111) face of nickel, and described intensity is measured by the X-ray diffraction analysis.

10. according to each jet head in the claim 1 to 9, the volume efficiency of orientation crystal face of ratio of peak intensity that wherein is defined as (111) face of the peak intensity of (200) face of nickel and nickel satisfies relations I (200)/I (111)＞1.0, wherein I (111) is the peak intensity of (111) face of nickel and the peak intensity of (200) face that I (200) is nickel, and described intensity is utilized the X-ray diffraction analysis and measured.

11. according to each jet head in the claim 1 to 10, wherein flow channel forms the content that element comprises sulphur and sulphur and is not more than 0.1% quality.

12. according to each jet head in the claim 1 to 11, wherein to form element be the nozzle plate that is configured to define nozzle to flow channel.

13. according to each jet head in the claim 1 to 12, wherein to form element be the flow passage plate that is configured to define fluid chamber to flow channel.

14. according to each jet head in the claim 1 to 13, wherein to form element be the oscillating plate with the element that is configured to define the fluid chamber wall surface to flow channel.

15. according to each jet head in the claim 1 to 14, comprise at least two and be selected from following element: the nozzle plate that is configured to define nozzle, be configured to define the flow passage plate of fluid chamber, with the oscillating plate with the element that is configured to define the fluid chamber wall surface, wherein said two elements form integral body.

16. according to each jet head in the claim 1 to 15, wherein flow channel forms element and forms by electrocasting.

17. according to each jet head in the claim 1 to 16, wherein to form the Vickers hardness of element be that 250 (Hv) are to 500 (Hv) to flow channel.

18. according to each jet head in the claim 1 to 17, it is a side inkjet type head, wherein the direction of liquid droplets is different from the direction of the flow channel that is used for recording liquid.

19. an imaging device comprises the record head of the drop that is configured to injection record liquid, wherein this record head is according to each jet head in the claim 1 to 18.

20. according to the imaging device of claim 19, wherein recording liquid is to comprise the printing ink of dyestuff as coloured material.

21. according to the imaging device of claim 19, wherein recording liquid is to comprise the printing ink of pigment as coloured material.

22. according to the imaging device of claim 19, wherein recording liquid is the printing ink that comprises polymer fine particles, comprises the granules of pigments as coloured material in this printing ink.

23. according to the imaging device of claim 19, wherein recording liquid is the printing ink that comprises BTA.

24. be configured to from the equipment of jet head liquid droplets, it comprises according to each jet head in the claim 1 to 18.

25. a recording method, wherein from drop according to each jet head injection record liquid the claim 1 to 18, thereby at the enterprising line item of recording medium.

26. according to the recording method of claim 25, wherein recording medium is the medium that is used to write down, it has support and the coating on the one side at least of support.

27. according to the recording method of claim 25 or 26, wherein being transferred to the amount of the recording liquid of recording medium during 100ms time of contact is 2-40ml/m ²And the amount that be transferred to the recording liquid of recording medium time of contact during 400ms is 3-50ml/m ², described amount is measured by dynamic scan liquid absorptiometer under 23 degrees centigrade and 50%RH.

28. according to the recording method of claim 25 or 26, wherein being transferred to the amount of the pure water of recording medium during 100ms time of contact is 2-45ml/m ²And the amount that be transferred to the pure water of recording medium time of contact during 400ms is 3-50ml/m ², described amount is measured by dynamic scan liquid absorptiometer under 23 degrees centigrade and 50%RH.

29. according to the recording method of claim 25, wherein to comprise the amount of the solid adhesion in base material and coating and the coating at least be 0.5-20.0g/m to recording medium ²

30. according to the recording method of claim 25, wherein the weight of recording medium is 50-250g/m ²

31., wherein recording medium is carried out supercalendering according to the recording method of claim 25.

32. according to each recording method in the claim 25 to 31, wherein recording medium comprises pigment and pigment is kaolin.

33. according to each recording method in the claim 25 to 31, wherein recording medium comprises pigment and pigment is powdered whiting.

34. according to each recording method in the claim 25 to 33, wherein recording medium comprises water-base resin.

35. according to the recording method of claim 34, wherein water-base resin is water-soluble resin or water-dispersed resin.

36. according to each recording method in the claim 25 to 35, wherein recording liquid comprises water at least, colouring agent, and wetting agent.

37. according to each recording method in the claim 25 to 36, wherein the surface tension of recording liquid under 25 degrees centigrade is 15-40mN/m.

38. according to each recording method in the claim 25 to 37, wherein to comprise dispersed colouring agent be 0.01-0.16 μ m as the average particulate diameter of colouring agent and dispersed colouring agent to recording liquid.

39. according to each recording method in the claim 25 to 38, wherein the viscosity of recording liquid under 25 degrees centigrade is 1-30mPasec.

40. according to each recording method in the claim 25 to 39, wherein recording liquid comprises surfactant and surfactant is a fluorine-containing surfactant.