CN101360799A

CN101360799A - Pigment dispersion and recording ink, and ink cartridge, ink jet recording method, and ink jet recording device

Info

Publication number: CN101360799A
Application number: CNA2006800515529A
Authority: CN
Inventors: 后藤宽; 松山彰彦; 永井希世文
Original assignee: Ricoh Co Ltd
Current assignee: Ricoh Co Ltd
Priority date: 2005-12-22
Filing date: 2006-12-15
Publication date: 2009-02-04
Anticipated expiration: 2026-12-15
Also published as: CN101360799B; JP2007169470A; JP4866079B2

Abstract

A pigment dispersion is provided that comprises a pigment, a pigment dispersant, a polymer dispersion stabilizer and water, wherein the polymer dispersion stabilizer is an alpha-olefin/maleic anhydride copolymer expressed by the formula (1) below. A recording ink is also provided that comprises the pigment dispersion, a surfactant, a water-dispersible resin, a humectant and water. in the structural formula (1), R represents an alkyl group and n is an integer of 30 to 100.

Description

Pigment dispersion, recording ink, print cartridge, ink jet recording method and ink-jet recording device

Technical field

The present invention relates under prolonged storage, to show excellent colo(u)rant dispersion stability pigment dispersion, be suitable for the recording ink of ink-vapor recording, and relate to print cartridge, ink jet recording method and ink-jet recording device.

Background technology

Recently, ink-jet printer is owing to its lower noise and lower running cost widespread use, and the color printer that can print on common paper is put goods on the market energetically.But, it is difficult satisfying whole general propertys for ink-jet printer, therefore described general property such as colorrendering quality, weather resistance, photostabilization, image dried performance, image do not have emergence (feathering) or do not have ink bleed (bleeding), duplex printing and discharge stability, consider the key property of various application and optionally use printing ink.

The printing ink that is used for ink-jet printer is usually based on water and contain tinting material such as dyestuff or pigment and wetting agent such as glycerine stop up preventing.From the color generation property and the stability of excellence, tinting material is generally dyestuff.But the photostabilization and the water tolerance of the image that is formed by the printing ink that contains dyestuff are relatively poor.Specifically, the water tolerance of this image is unsatisfactory on common paper, but has the improvement that has on the special-purpose ink jet recording paper of ink absorbing layer to a certain degree.

In order to address these problems, recently, studied alternative recording ink, wherein will replace the pigment of dyestuff such as organic pigment and carbon black with tensio-active agent or dispersion agent micronization, and be distributed in medium such as the water.For example, patent documentation 1 and 2 discloses by becoming particle diameter 50nm to improve the method for jetting stability to get off the pigment dyestuff micronization with specific dispersant.Patent documentation 3 discloses and has used the specific pigment dyestuff and the ink for inking of anionic dispersing agents.

But, no matter any dispersion agent all can not change into the pigment dyestuff micro mist primary particle diameter that is lower than them.In addition, the granularity that is difficult under the situation of deterioration tone not pigment dyestuff is reduced to below the 50nm.In addition, under the situation of using the lower pigment dispersing agent of molecular weight, there is such problem, i.e. colo(u)rant dispersion less stable, pigment may be assembled with the aqueous solvent in the printing ink; Under the situation of using the lower pigment dispersing agent of molecular weight, dispersed possibility is variation owing to the viscosity higher of pigment dispersion.Also there is such problem, promptly uses printed matter deficiency aspect scratch resistance and water tolerance of these printing ink.

Owing to ink-vapor recording requires ink droplet stable discharge from the micro-nozzle of ink jet print head, so this printing ink must can not solidify because of locating drying in the hole of ink jet print head fully.But, being used under the situation of ink-vapor recording at the printing ink that disperses pigment dyestuff, dispersing of pigments stability especially can reduce under prolonged storage, and therefore, the pigment gathering that is brought can cause the obstruction of ink jet print head injection nozzle or printing ink not to spray.Particularly when ending to print, spray nozzle clogging may take place when long-term, and the printing ink of retrogradation can be deposited in attending device such as nozzle cap or the suction pipe, this may hinder the function of attending device.In addition, when printing is supspended or ended because of the blank in the print file or single file blank short period of time, following problem often appears, as the printing failure that causes because of the distortion of ink droplet jet direction or intermittently discharge failure.

Other dispersing method as pigment dyestuff, so-called surface modification recording ink has been proposed, wherein do not having by the granules of pigments surface modification being become hydrophilic mode, pigment stably to be disperseed under the situation of anionic dispersing agents with carboxyl, carbonyl, sulfuryl, hydroxyl etc.As black recording printing ink, for example, developed so-called surface-modified carbon black, wherein do not having under the situation of anionic dispersing agents, by introduce the mode of hydrophilic radical on the surface of carbon, carbon black is stably disperseed.In addition,, developed so-called surface modification coloured pigment, wherein do not had under the situation of anionic dispersing agents coloured pigment stably to be disperseed as the printing ink of coloured pigment.But these surface modification recording inks lack scratch resistance usually on common paper or special-purpose glossy paper, and have poor water tolerance,

In order to address the above problem, proposed to contain the ink for inking of micro-capsule or emulsion, wherein granules of pigments is coated with resin.According to this scheme, because granules of pigments is coated with resin securely, dispersion can be steady in a long-term, and jetting stability can be improved; But, make that to disperse particle diameter be to be expensive and difficult below the 150nm, promptly using the resin-coating primary particle diameter also is like this as 50nm to the pigment of 100nm.

Patent documentation 4 and 5 has been described a kind of scheme, wherein by on the surface of metal oxide, making tinting material have nanometer particle size the mode of its coating with the organic compound with ionic group then deposition of dye and uniform grain sizes distributes, and the gained tinting material can be used for ink for inking.According to this scheme, to compare with the printing ink that uses dyestuff, water tolerance can be improved; But photostabilization is easy to poorer than the printing ink that uses dyestuff, so gained printing ink is unsuitable for actual use.

So, using dispersion agent dispersed color or surface of pigments to be processed under the hydrophilic situation, resin can added the shortage of printing ink with compensation water tolerance and scratch resistance; But, when using water-soluble polymers, can not obtain enough water tolerance usually.For this reason, proposed to use the method for water-dispersed resin; But because the resin particle of printing on the record thing can be easy to redispersion in water, so water tolerance is still not enough.

Recently, proposed composite pigment, wherein pigment dyestuff is coated on the inorganic pigment granules.When the inorganic pigment granules when about 5 to 50nm is used as core material, when promptly using pigment dyestuff to apply, still can obtain colorant pigment (referring to patent documentation 6 and 7) less than 100nm.10 to 20nm composite pigment tinting material can obtain from market.Also proposed these composite pigment particles are applied to coating or ink for inking, as disclosed in patent documentation 8 and 9.But because do not contain fixing resin, these composite pigment particles still suffer relatively poor dispersion stabilization, especially under prolonged storage, and print insufficient water tolerance of article and scratch resistance.

Also proposed to contain the ink composite of resin, for example, contained the pigment that is dispersed in the water and the printing ink of water-dispersed resin, as disclosed in patent documentation 10; The printing ink that contains the pigment in the polymer emulsion dispersion that is dispersed in water soluble resin is as disclosed in patent documentation 11; The printing ink that has the emulsion of specific film-forming temperature with use is as disclosed in patent documentation 12.

In addition, also have many about adding polymeric dispersant to improve the scheme of composite pigment particulate crystallized ability, as disclosed in patent documentation 9,13,14,15,16,17,18 and 19.In these schemes, polymeric dispersant is expected to strengthen crystallized ability.But though scratch resistance may be improved fully, these polymeric dispersants suffer insufficient water tolerance because of they water-soluble usually.

Therefore, need such material recently, as can under prolonged storage, showing the pigment dispersion of excellent colo(u)rant dispersion stability; The recording ink that contains this pigment dispersion, it can show excellent jetting stability and not have head to stop up when printing, it can bring excellent image durability such as water tolerance and photostabilization, it can provide the high-quality image that not only all has excellent tone at specific record paper but also on common paper, and it is applicable to ink-vapor recording; And relevant technology.

For the printing ink of the ink-vapor recording that is used for family and office, use water color ink usually based on water, it contains tinting material, wetting agent such as glycerine, penetrant with perviousness, tensio-active agent and other the optional additive of control to recording paper.

The water color ink of ink-vapor recording is penetrated into by water color ink normally that recording medium fixes; therefore; developed special-purpose ink jet recording paper, it has receptivity, crystallized ability that colouring component is strengthened on paper surface, and to the protective capability of colouring component.But special-purpose ink jet recording paper is more expensive, and this is because its manufacturing processed comprises the coating procedure after the multiple papermaking, and owing to contain many processing chemical aspect the ability of recovery than common paper difference; In this case, enough picture quality that at present need be on common paper.

Common paper is compared with special-purpose ink jet recording paper, it is complementary to have poor absorption of inks ability and lower ink performance, therefore, there is following problem in record on common paper, ink bleed, the decline of (3) density, the decline of (4) chromophoric characteristic, the decline of (5) water tolerance, the decline of (6) photostabilization, (7) gasproof decline, the decline of (8) fixed performance, (9) printing ink print through etc. occur as (1) appearance emergence, (2).It is very important addressing these problems to carry out ink-vapor recording on common paper.

In recent years, by improving pigment-dispersing and/or littleization particle diameter, pigment is through being usually used in ink for inking.By improving from dispersion stabilization, promptly except the conventional pigment dispersion that uses tensio-active agent and/or water soluble resin, also give wetting ability by carrying out surface modification as the mode of carrying out oxidation, sulfonation or graft polymerization on surface of pigments, dispersing of pigments is improved.These pigment can improve above-mentioned (5), (6) and (7); The concentration of modified pigment and tinctorial property are poorer than dyestuff, and also poor than dye ink of the jetting stability of this pigment ink, prolonged storage and redispersibility.Therefore, as under the situation of tinting material, it is important improving ink density, color development (color development) and reliability at pigment.In order to address these problems, for example, a lot of ink for ink-jet recording have been proposed, it contains colored polymer beads, especially polyester emulsion or based on the polymer beads (referring to patent documentation 20, non-patent literature 1) of vinyl.These schemes adopt the printing ink that contains the resin dispersion that comprises tinting material, and wherein tinting material is included in water-fast, the water-dispersed resin.When colored pigment dyestuff was used as tinting material, on common paper, image density under the conventional ink formulations and colorrendering quality were better than the pigment ink with water soluble dispersing agent.

Up to now, studied the infiltrative control that printing ink is entered paper, sprouted wings and ink bleed, improved print density and color development and suppress print through to reduce.A kind of super perviousness ink for inking can obtain from market, and its surface tension adjustment is to be lower than 35mN/m enters paper with raising perviousness.This printing ink reduce ink bleed effectively and be easy on common paper dry, exist simultaneously not enough, as sprout wings, lower print density and lower print quality.On the other hand, a kind ofly permeate slow ink for inking and also can obtain from market, thereby its surface tension adjustment is to be higher than 35mN/m to slow down to the infiltration of paper and make printing ink remain on the surf zone of paper, and this can reduce emergence effectively, improve print density and color development, and reduces print through.

But lower perviousness has reduced the drying power after printing on the common paper significantly, therefore, causes the crystallized ability deterioration and/or at ink bleed between color under the situation of multi-color printing.Consider these problems, developed and used the compound oil ink group, thereby wherein permeate slow printing ink and super perviousness printing ink in conjunction with guaranteeing picture quality with the ink bleed that suppresses between color.But, carrying out under the situation of duplex printing, need for some time after printing, to wait for ink setting with the slow printing ink of infiltration, this makes the productivity variation of duplex printing.Also have a kind of type printer that can obtain from market, its equipment that is equipped with heating paper before and after printing is to improve ink setting ability (referring to patent documentation 21).But the shortcoming of this device is big and complicated system, and because of additional heating installation causes wasted heat, this has eliminated the advantage of ink-vapor recording.

Except these schemes, also ink for inking various researchs have been carried out aspect reliability and the picture quality.Need prevent that ink viscosity from improving to suppress the injector head obstruction.For example, patent documentation 22 discloses the printing ink blank and can prevent in the following manner: compare before and after the concentration of printing ink concentrates twice, viscosity is changed to be controlled at be lower than 10 times and vary in diameter and be lower than 3 times, sprawl thereby make pigment suppress printing ink.But this printing ink is difficult to produce high quality graphic on common paper.

Patent documentation 23 discloses a kind of printing ink, and wherein the resistates after the volatile constituent evaporation is a liquid in the printing ink, and the viscosity of this resistates is lower than 10 times of initial viscosity.Therefore but this printing ink is a kind of printing ink that contains dyestuff, although higher reliability is arranged but still poor picture quality may be provided.

Patent documentation 24 discloses a kind of printing ink, wherein compares before and after 60 ℃ of following water evaporations, and the viscosity increase is lower than 600 times.But this printing ink also is a kind of printing ink that contains dyestuff, although therefore be intended to improve reliability and weather resistance by adding water-soluble polymers, water tolerance is still not enough.

It is that 5 to 15mPas printing ink is to guaranteeing that higher quality is suitable that patent documentation 25 discloses viscosity.The document discloses and can advantageously add certain compound to regulate initial evaporation rate and to be that reliability is provided with viscosity; From containing the printing ink of pigment, the scheme of these may propose to deal with problems (3) and (4).But the document does not comprise the explanation of the particle size stable of pigment, that is to say, this printing ink may lack reliability according to shower nozzle and/or jet size under prolonged storage, though it may be stable after 24 hours in storage.

As mentioned above, must use high viscosity inks to print, simultaneously, be difficult to guarantee the reliability of high viscosity inks to guarantee the high quality under fair speed.

Patent documentation 10 and 11 discloses water soluble resin has been joined pigment ink to improve picture quality.Patent documentation 26 discloses and used the ratio of pigment and resin emulsion wherein is that the median size of 1: 0.1 to 1: 1 and coloring components is that the printing ink of 0.3 to 1.2 μ m can improve the image on the common paper.This printing ink that contains resin emulsion can suppress to sprout wings by reducing ink bleed, still, because insufficient image density and may lack reliability as ink for inking.As the improvement to reliability, patent documentation 27 discloses a kind of printing ink, and wherein a kind of water-fast material joins this printing ink and minimum film-forming temperature is more than 40 ℃; Patent documentation 28 discloses a kind of printing ink, and wherein the particle size of emulsion that is added is no more than 50nm.But, the reliability of these printing ink may be still unsatisfactory and picture quality still not enough.Patent documentation 29 discloses by use and has contained pigment, carbohydrate and derivative thereof, contains the polyvalent alcohol of 5 above hydroxyls and the printing ink of resin emulsion improves the printing ununiformity.This printing ink is easy to show the lower perviousness that enters common paper and is having problems aspect emergence and/or ink bleed, crystallized ability and time of drying.Patent documentation 30 discloses a kind of by water-dispersed resin and the printing ink formed from dispersed color, and wherein solid content is 1.0 to 16 quality %, and the picture quality on common paper is improved.Compare with the printing ink that contains dyestuff, this scheme can cause higher water tolerance; But under the situation of frequent applying marking pen, the image on the common paper keeps the performance possibility not enough.

In addition, viscosity when pigment dispersion and resin emulsion join printing ink has been improved and solid content improves and carried out many researchs.For example, patent documentation 29 and 31 discloses ink formulations, although wherein improved solid content by the mode that adds the resin that can form micellar aggregates, viscosity improves not highly significant.But these schemes suffer the lower picture quality that causes because of insufficient perviousness on the common paper.Can absorb by capillary the perviousness of paper and to explain by the Lucas-Washburn The Representation Equation; And viscosity is high more, and is low more for realizing the contact angle between the required surface tension of enough perviousness low more and/or paper and printing ink.Patent documentation 32 and 33 proposes polyol alkyl ether is added the printing ink of higher solids content to improve perviousness; But, these schemes suffer under viscosity improves when solid content improves the situation because of insufficient perviousness cause than low image quality.

Be well known that, even organic silicon surfactant and fluorochemical surfactant also can improve perviousness under trace, and in the prior art the application to them study.For example, patent documentation 34 and 35 has proposed to have the ink for inking of fluorochemical surfactant; Patent documentation 36 and 37 has proposed to have the printing ink of pigment dispersion and fluorochemical surfactant.Patent documentation 38 has also proposed the printing ink that viscosity is not less than 5mPas, and it comprises fluorochemical surfactant and by polymer fine particles and water insoluble or be insoluble in the polymer emulsion that the coloured material of water forms.But these schemes suffer that pigment content improves in tonal variation and the printing ink, therefore, are difficult to obtain favourable tone under higher pigment content, and may be not enough at water tolerance and crystallized ability under the situation of dispersed color.

Patent documentation 1: open in advance (JP A) No.09-263720 of Japanese patent application

Patent documentation 2:JP-A No.09-263722

Patent documentation 3:JP-A No.2002-88286

Patent documentation 4:JP-A No.11-166127

Patent documentation 5:JP-A No.2001-192582

Patent documentation 6:JPA No.2002-146231

Patent documentation 7:JP-A No.2002-161221

Patent documentation 8:JP-A No.2003-49096

Patent documentation 9:JP-A No.2003-55591

Patent documentation 10: Japanese Patent Application Publication (JP-B) No.62-1426

Patent documentation 11:JP-A No.55-157668

Patent documentation 12:JP-A No.01-217088

Patent documentation 13:JP A No.2003-49096

Patent documentation 14:JP-A No.2003-105229

Patent documentation 15:JP-A No.2003-171594

Patent documentation 16:JP-A No.2003-192938

Patent documentation 17:JP-A No.2003-327866

Patent documentation 18:JP-A No.2003-268278

Patent documentation 19:JP-A No.2003-327880

Patent documentation 20:JP-A No.2000-191972

Patent documentation 21:JP-A No.55-69464

Patent documentation 22:JP-A No.2002-337449

Patent documentation 23:JP-A No.2000-095983

Patent documentation 24:JP-A No.09-111166

Patent documentation 25:JP-A No.2001-262025

Patent documentation 26:JP-A No.04-332774

Patent documentation 27: Japanese Patent (JP-B) No.2867491

Patent documentation 28:JP-A No.04-18462

Patent documentation 29:JP-B No.3088588

Patent documentation 30:JP-A No.2004-35718

Patent documentation 31:JP-A No.2004-99800

Patent documentation 32:JP-A No.2004-155867

Patent documentation 33:JP-A No.2004-203903

Patent documentation 34:JP-B No.2675001

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Non-patent literature 1: the functional pigment The Application of Technology is promoted (Applied Expansion ofFunctional Pigments Technology), CMC Co., Ltd.

Summary of the invention

Purpose of the present invention first is to provide a kind of pigment dispersion that shows superior dispersion stability under prolonged storage; A kind of recording ink, it uses this pigment dispersion and is suitable for ink-vapor recording, it shows excellent jetting stability and does not have head to stop up, provide to have excellent weather resistance such as water tolerance and sunproof image, and form the high quality graphic that not only on specific record paper but also on common paper, all has suitable tone; A kind of print cartridge of this recording ink, a kind of ink jet recording method and a kind of ink-jet recording device of using.

Purpose of the present invention second is to provide a kind of recording ink, it provides picture quality excellent on the common paper and does not have the printing ink blank, and have higher image density, color saturation, weather resistance such as water tolerance and photostabilization, and show on glossy paper excellent drying property and pearlization (beading), excellent rate of drying and flying print, reach suitable nozzle ejection stability; And the print cartridge, ink jet recording method and the ink-jet recording device that use this recording ink.

These purposes can obtain through the following description of the present invention.

In first aspect, the invention provides a kind of pigment dispersion, it comprises pigment, pigment dispersing agent, polymeric dispersion stabilizer and water,

Wherein polymeric dispersion stabilizer is the alpha-olefin/copolymer-maleic anhydride of following formula (1) expression:

Formula (1)

In formula (1), R represents that alkyl and n are 30 to 100 integer.

Preferably, the acid number of this alpha-olefin/copolymer-maleic anhydride is 100 to 400mgKOH/g.

Preferably, this alpha-olefin/copolymer-maleic anhydride uses as the solution in basic solution or alkaline aqueous solution, and in this basic solution or the alkali number in this alkaline aqueous solution be not less than the alkali number suitable with the acid number of this alpha-olefin/copolymer-maleic anhydride.

Preferably, this pigment is pigment dyestuff or the composite pigment that has applied the mineral dye of pigment dyestuff.

Preferably, this pigment dyestuff is to be selected from a kind of in phthalocyanine pigment, quinacridone pigment and the monoazo yellow pigment.

Preferably, this inorganic pigment granules is to be selected from least a in titanium dioxide granule, silica dioxide granule, alumina particle, ferric oxide particles, iron hydroxide particle and the granules of stannic oxide.

Preferably, this pigment dispersing agent is that anion surfactant and HLB value are a kind of in 10 to 20 the nonionic surface active agent.

Preferably, the median size D of pigment dispersion ₅₀Be not more than 150nm.

On the other hand, the invention provides a kind of recording ink, it comprises above-mentioned pigment dispersion, tensio-active agent, water-dispersed resin, wetting agent and water.

Preferably, this tensio-active agent is a kind of in organic silicon surfactant and the fluorochemical surfactant.

Preferably, this water-dispersed resin shows the film forming ability after printing on the recording medium, and has and be not higher than 30 ℃ minimum film-forming temperature.

Preferably, this wetting agent is for being selected from glycerine, glycol ether, triglycol, 1,3 butylene glycol and 3-methyl isophthalic acid, at least a in the 3-butyleneglycol.

Preferably, this recording ink also comprises the pH regulator agent, and it is to be selected from least a in hydramine, alkali metal hydroxide, ammonium hydroxide, phosphonium hydroxides and the alkaline carbonate, and the pH value of this recording ink is 7 to 11.

In a further aspect, the invention provides a kind of recording ink, it comprises water dispersible tinting material, water-dispersed resin, wetting agent and water at least,

Wherein this water dispersible tinting material is the pigment dispersion that comprises pigment, pigment dispersing agent and polymeric dispersion stabilizer,

This polymeric dispersion stabilizer is the alpha-olefin/copolymer-maleic anhydride by following formula (1) expression, or at least a mixture in this alpha-olefin/copolymer-maleic anhydride and styrene/acrylic analog copolymer, water soluble polyurethane resin and the Polyester Resin Water Soluble

The content of this wetting agent in recording ink is 20 to 35 quality %, and the ratio (A/B) that the solid content (A) of this water-dispersed resin in this printing ink and the solid content (B) of this pigment in this water dispersible tinting material satisfy them is 2 to 8 relation,

Formula (1)

In formula (1), R represents alkyl, and n is 30 to 100 integer.

More on the one hand in, the invention provides a kind of recording ink, it comprises water dispersible tinting material, water-dispersed resin, wetting agent and water at least,

Wherein this water dispersible tinting material is the pigment dispersion that comprises pigment and polymeric dispersion stabilizer,

This pigment carries hydrophilic radical from the teeth outwards at least, and is not having to show as water dispersible or water miscible from dispersed color under the situation of dispersion agent,

The content of this wetting agent in recording ink is 20 to 35 quality %, and solid content (A) and this pigment solid content (B) in this water dispersible tinting material the ratio (A/B) that satisfy they of this water-dispersed resin in this printing ink is 2 to 8 relation,

Formula (1)

In formula (1), R represents alkyl, and n is 30 to 100 integer.

Preferably, based on whole recording ink, the total content of this water dispersible tinting material and this water-dispersed resin is 12 to 40 quality %.

Preferably, the matter average molecular weight of this alpha-olefin/copolymer-maleic anhydride is not higher than 20000.

Preferably, the acid number of this alpha-olefin/copolymer-maleic anhydride is 100 to 400mgKOH/g, and use as the solution in basic solution or alkaline aqueous solution, this basic solution or alkaline aqueous solution contain and are not less than the alkali number suitable with the acid number of this alpha-olefin/copolymer-maleic anhydride.

Preferably, this HLB value is that 10 to 20 nonionic surface active agent is polyoxyethylene betanaphthyl ether, polyoxyethylene lauryl ether and polyoxyethylene vinylbenzene phenyl ether.

Preferably, this water-dispersed resin is a kind of in vibrin, urethane resin, acrylic resin and the acrylic acid or the like silicone resin, and the minimum film-forming temperature of this water-dispersed resin is not for being higher than 30 ℃.

Preferably, this recording ink also comprises surfactant, and this tensio-active agent comprises and is selected from least a in organic silicon surfactant and the fluorochemical surfactant.

Preferably, this recording ink the viscosity under 25 ℃ be 5 to 20mPas and surface tension under 25 ℃ for not being higher than 35mN/m.

More on the one hand in, the invention provides print cartridge, it comprises above-mentioned recording ink in container.

More on the one hand in, the invention provides ink jet recording method, it comprises the ink jet step at least, wherein in this ink jet step, applies stimulation with by the injection record image to above-mentioned recording ink.

Preferably, this stimulation is to be selected from least a in heat, pressure, vibration and the light.

More on the one hand in, the invention provides ink-jet recording device, it comprises the ink jet unit at least, wherein applies stimulation with by the injection record image by this ink jet unit to above-mentioned recording ink.

More on the one hand in, the invention provides ink recorded matter, it comprises the image that is formed by above-mentioned recording ink on recording medium.

Pigment dispersion according to the present invention comprises pigment, pigment dispersing agent, polymeric dispersion stabilizer and water, and wherein this polymeric dispersion stabilizer is the alpha-olefin/copolymer-maleic anhydride by following formula (1) expression.The combination of these compositions can improve the dispersion stabilization of pigment under prolonged storage, so this pigment dispersion can be especially with the tinting material that acts on ink-jet recording ink.

In the first embodiment, recording ink according to the present invention comprises according to pigment dispersing agent of the present invention, tensio-active agent, water-dispersed resin, wetting agent and water.Can bring following advantage by pigment dispersion according to the present invention according to recording ink of the present invention: excellent jetting stability and obstruction without a head when printing, image with excellent in water resistance and sunproof height weather resistance, and not only at specific record paper but also on common paper, all have the high quality graphic of favourable tone.

Print cartridge according to the present invention contains the recording ink of first embodiment of the invention in container.This print cartridge can be used for the printer of ink jet recording method etc. suitably.In this print cartridge, use the record of this printing ink can bring excellent jetting stability and obstruction without a head when printing, image with excellent in water resistance and sunproof height weather resistance, and not only at specific record paper but also on common paper, all have the high quality graphic of favourable tone.

Ink-jet recording device of the present invention comprises the ink jet unit at least, and its recording ink that energy is applied to first embodiment of the invention is to pass through to spray this recording ink document image.In this ink-jet recording device, thereby apply energy and from the nozzle ejection document image to recording ink of the present invention.The result, printing can be carried out under following situation: excellent jetting stability and do not have head to stop up, image can form has high-durability such as water tolerance and photostabilization, not only at specific record paper but also all have the high quality graphic of favourable tone on common paper.

Ink jet recording method of the present invention comprises the ink jet step at least, and the recording ink that wherein energy is applied to first embodiment of the invention is to pass through to spray this recording ink document image.In this ink jet recording method, thereby apply energy and from the nozzle ejection document image to recording ink of the present invention.The result, printing can be carried out under the jetting stability of excellence and not have head to stop up, image can form has high-durability such as water tolerance and photostabilization, not only can form the high quality graphic with favourable tone at specific record paper but also on common paper.

Ink recorded matter according to the present invention comprises the image that the recording ink by first embodiment of the invention forms on recording medium.Can form image with following situation on this ink recorded matter: excellent jetting stability and obstruction without a head when printing, have excellent in water resistance and sunproof height weather resistance, and not only at specific record paper but also on common paper, all have the high quality of favourable tone.

In second embodiment, recording ink of the present invention comprises the water dispersible tinting material at least, water-dispersed resin, wetting agent and water, wherein this water dispersible tinting material is for comprising pigment, the pigment dispersion of pigment dispersing agent and polymeric dispersion stabilizer, this polymeric dispersion stabilizer is the alpha-olefin/copolymer-maleic anhydride of following formula (1) expression, or this alpha-olefin/copolymer-maleic anhydride and styrene/acrylic analog copolymer, at least a mixture in water soluble polyurethane resin and the Polyester Resin Water Soluble, the content of this wetting agent in recording ink is 20 to 35 quality %, and solid content (A) and this pigment solid content (B) in this water dispersible tinting material the ratio (A/B) that satisfy they of this water-dispersed resin in this printing ink is 2 to 8 relation.

In the 3rd embodiment, recording ink of the present invention comprises the water dispersible tinting material at least, water-dispersed resin, wetting agent and water, wherein this water dispersible tinting material is the pigment dispersion that comprises pigment and polymeric dispersion stabilizer, this pigment carries hydrophilic radical from the teeth outwards at least, and do not having to show as water dispersible or water miscible under the situation of dispersion agent from dispersed color, this polymeric dispersion stabilizer is the alpha-olefin/copolymer-maleic anhydride by above-mentioned formula (1) expression, or this alpha-olefin/copolymer-maleic anhydride and styrene/acrylic analog copolymer, at least a mixture in water soluble polyurethane resin and the Polyester Resin Water Soluble, the content of this wetting agent in recording ink is 20 to 35 quality %, and solid content (A) and this pigment solid content (B) in this water dispersible tinting material the ratio (A/B) that satisfy they of this water-dispersed resin in this printing ink is 2 to 8 relation.

The recording ink of the second or the 3rd embodiment can be provided in picture quality excellent on the common paper, particularly do not have the printing ink blank and have higher image density, color saturation, weather resistance such as water tolerance and photostabilization, and on glossy paper, show excellent drying property and pearlization, excellent rate of drying and flying print, and suitable nozzle ejection stability.

Print cartridge of the present invention contains the recording ink of the present invention second or the 3rd embodiment in container.This print cartridge can be used for the printer of ink jet recording method etc. suitably.The record of this printing ink of use can bring the picture quality of the excellence on common paper in this print cartridge, particularly do not have the printing ink blank and have higher image density, color saturation, weather resistance such as water tolerance and photostabilization, and on glossy paper, show excellent drying property and pearlization, excellent rate of drying and flying print, and suitable nozzle ejection stability, therefore, can write down the image that has as the high definition of printed matter.

Ink-jet recording device of the present invention comprises the ink jet unit at least, and its recording ink that energy is applied to the present invention second or the 3rd embodiment is to pass through to spray this recording ink document image.In this ink-jet recording device, thereby apply energy and from the nozzle ejection document image to recording ink of the present invention.The result, this record can bring the picture quality of the excellence on common paper, particularly do not have the printing ink blank and have higher image density, color saturation, weather resistance such as water tolerance and photostabilization, and on glossy paper, show excellent drying property and pearlization, excellent rate of drying and flying print, and suitable nozzle ejection stability, therefore, can write down the image that has as the high definition of printed matter.

Ink jet recording method of the present invention comprises the ink jet step at least, and the recording ink that wherein energy is applied to the present invention second or the 3rd embodiment is to pass through to spray this recording ink document image.In this ink jet recording method, thereby apply energy and from the nozzle ejection document image to recording ink of the present invention.The result, this record can bring the picture quality of the excellence on common paper, particularly do not have the printing ink blank and have higher image density, color saturation, weather resistance such as water tolerance and photostabilization, and on glossy paper, show excellent drying property and pearlization, excellent rate of drying and flying print, and suitable nozzle ejection stability, therefore, can write down the image that has as the high definition of printed matter.

Ink recorded matter of the present invention is included on the recording medium image that the recording ink by the present invention second or the 3rd embodiment forms.Should can not have the printing ink blank and have higher image density, color saturation, weather resistance such as water tolerance and photostabilization by the ink recorded matter on common paper, and on glossy paper, show excellent drying property and pearlization, excellent rate of drying and flying print, and suitable nozzle ejection stability, therefore, can on recording medium, write down the image that has as the high definition of printed matter.

Description of drawings

Fig. 1 is the illustrative example figure according to print cartridge of the present invention.

Fig. 2 is the print cartridge of Fig. 1 and the synoptic diagram of shell thereof.

Fig. 3 is the perspective schematic view of the print cartridge mounting portion of ink-jet recording device, the wherein covered opening of this device.

Fig. 4 is the synoptic diagram that shows the whole structure of ink-jet recording device.

Fig. 5 is the schematic enlarged view that exemplarily shows according to ink gun of the present invention.

Embodiment

Pigment dispersion

Pigment dispersion according to the present invention comprises pigment, pigment dispersing agent, polymeric dispersion stabilizer, He Shui, and also comprises other optional component as required.

Polymeric dispersion stabilizer

Polymeric dispersion stabilizer can be for showing the alpha-olefin/copolymer-maleic anhydride of structural formula (1) expression down.

Formula (1)

In this structural formula (1), R represents alkyl, and the carbonatoms of this alkyl is preferably 6 to 25, more preferably 6 to 22, and this alkyl can be straight chain, branched or cyclic; N is 30 to 100 integer.

Alpha-olefin/the copolymer-maleic anhydride of this structural formula (1) expression at room temperature is solid and can be almost water-soluble not at all usually.This alpha-olefin/copolymer-maleic anhydride is stable pigment dispersions effectively, and pigment is finely divided equably in water in this pigment dispersion.When this alpha-olefin/copolymer-maleic anhydride was dissolved in this alkalescence or alkaline aqueous solution under the alkali number of alkalescence or alkaline aqueous solution is not less than the condition of the alkali number suitable with the acid number of this alpha-olefin/copolymer-maleic anhydride, the effect of stabilising dispersions was remarkable.

This alpha-olefin/copolymer-maleic anhydride can be easy to be dissolved in alkalescence or alkaline aqueous solution in heating with under stirring.Under some long situation of the alkene chain of this multipolymer, can be difficult to dissolve this multipolymer, so insolubles can remain in the solution; In this case, can be only by insolubles being removed and effectively use this multipolymer with strainer etc.

The example of alkali comprises in alkalescence or the alkaline aqueous solution: alkali metal hydroxide such as sodium hydroxide, potassium hydroxide and lithium hydroxide; Alkaline matter such as ammoniacal liquor, triethylamine and morpholine; Hydramine such as trolamine, diethanolamine, N methyldiethanol amine, 2-amino-2-ethyl-1, ammediol and choline.

The acid number of this alpha-olefin/copolymer-maleic anhydride is preferably 100 to 400mgKOH/g, more preferably 100 arrives 350mgKOH/g.When this acid number was lower than 100mgKOH/g, the solubleness in basic solution can be not enough, and when this acid number was higher than 400mgKOH/g, ink jet can be interfered because of the higher viscosity of dispersion, and perhaps dispersion stabilization can variation.

The matter average molecular weight of this alpha-olefin/copolymer-maleic anhydride is preferably 5000 to 20000.When this matter average molecular weight less than 5000 the time, the dispersion stabilization of pigment dispersion can reduce, and when this matter average molecular weight greater than 20000 the time, the solubleness in basic solution can be not enough, perhaps viscosity can be inappropriate high.

Polymeric dispersion stabilizer can suitably synthesize or buy from market; The example comprises T-YP110, T-YP111, T-YP112 and T-YP113 (Seico PMC Co. system).

Based on the pigment in solid content of 100 mass parts, the amount of polymeric dispersion stabilizer is preferably 1 to 100 mass parts, more preferably 5 to 50 mass parts.When this measured less than 1 mass parts, the dispersion temperature effect can be ignored, and when this measured greater than 100 mass parts, ink jet can be hindered because of higher viscosity, and perhaps cost can be higher.

Pigment

Pigment optimization is a composite pigment, and it forms by applying pigment dyestuff or sooty organic or inorganic granules of pigments.This composite pigment can by with pigment dyestuff or carbon deposition on inorganic pigment granules or by mineral dye being mixed with mineral dye or carbon black mechanochemistry and grinding and produce.Bounding force between pigment dyestuff and mineral dye can be as required by layer improving of the polysiloxane that formed by alkyl silane or organic silane compound is set between them.

The example of pigment dyestuff comprises the nigrosine as black pigment; Anthraquinone, phthalocyanine blue, phthalocyanine green, diazonium or monoazo yellow pigment, disazo yellow pigment, pyranthrone (pyranthoron), perylene, heterocyclic yellows, quinacridone, (sulphur) indigo etc. as coloured pigment.Wherein, from the color development ability, phthalocyanine pigment, quinacridone pigment, monoazo yellow pigment, disazo yellow pigment and heterocyclic yellow pigments are particularly preferred.

3,15:4), aluminum phthalocyanine etc. the example of phthalocyanine pigment comprises: copper phthalocyanine blue and derivative thereof (CI. pigment Blue 15:.

The example of quinacridone pigment comprises: C.I. pigment orange 48, C.I. pigment orange 49, C.I pigment red 122, C.I. Pigment red 192, C.I. Pigment red 202, C.I. Pigment red 206, C.I. Pigment Red 207, C.I. Pigment red 209, C.I. pigment violet 19, C.I. pigment violet 42 etc.

The example of monoazo yellow pigment comprises: C.I. Pigment Yellow 73 74, C.I. Pigment Yellow 73 109, C.I. pigment Yellow 12 8, C.I. Pigment Yellow 73 151 etc.

The example of disazo yellow pigment comprises: C.I. pigment Yellow 14, C.I. Pigment Yellow 73 16, C.I. pigment yellow 17 etc.

The example of heterocyclic yellow pigments comprises: C.I. Pigment Yellow 73 117, C.I. pigment yellow 13 8 etc.

Other tinting pigment can be referring to " color index (The Color Index), the third edition, dyer's dyer association (1982) ".

The example of inorganic particle comprises titanium dioxide, silicon-dioxide, aluminum oxide, ferric oxide, ironic hydroxide, stannic oxide etc.These can be used alone or in combination.

Preferred organic pigment particle has the particle shape of low long-width ratio, and is more preferably spherical.The color of inorganic pigment granules is preferably transparent or white under the situation of this pigment coloring, and black inorganic pigment also can allow under the situation of deposition black colorant.The primary particle diameter of inorganic pigment granules is preferably and is not more than 100nm, more preferably 5 arrives 50nm.

Inorganic pigment granules with as pigment dyestuff or sooty mass ratio, the i.e. inorganic pigment granules of coloured material: coloured material is preferably 3: 1 to 1: 3 and more preferably 3: 2 to 1: 2.When the mass ratio of painted material hour, color development ability or tinting strength can deteriorations, and when the amount of painted material is too high, transparency or tone are understood deterioration.

Wherein inorganic pigment granules comprises matrix material such as silicon-dioxide/carbon black composite material, silicon-dioxide/phthalocyanine C.I.PB 15:3 matrix material, silicon-dioxide/dual-azo yellow matrix material and silicon-dioxide/quinacridone C.I.PR122 matrix material (TodaKogyo Co. system) with the example of the color grains of pigment dyestuff or carbon black coating.The primary particle diameter of these materials is small enough to favourable use.

When elementary particle diameter is the inorganic pigment granules of 20nm when applying with the pigment dyestuff of equivalent, the primary particle diameter strain of this pigment is about 25nm.When these pigment can be dispersed into their primary granule with suitable dispersion agent, can produce the dispersion particle diameter was the printing ink that is dispersed with superfine pigment of 25nm.In these composite pigments, not only lip-deep pigment dyestuff influences dispersion, and the performance of the mineral dye at center also embodies by the thick thin layer of 2.5nm, the selection of pigment dispersing agent should be based on this organic and mineral dye.

In the present invention, it is hydrophilic to become that the colorant pigment particle can carry out surface treatment with carboxyl, carbonyl, sulfo group, hydroxyl etc., can use its aqueous dispersion then.Surface-treated technology can be those of routine, as oxide treatment, azo reaction and plasma treatment.

Pigment dispersing agent

Be used to disperse the pigment dispersing agent of pigment dyestuff or composite pigment to be preferably the nonionic surface active agent of anion surfactant or HLB value 10 to 20.

The example of anion surfactant comprises Voranol EP 2001 acetic ester, alkylbenzene sulfonate (NH for example ₄, Na, Ca), alkyl diphenyl base ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate (NH for example ₄, Na, Ca), dialkyl succinate sodium sulfonate, naphthene sulfonic acid formalin condenses sodium salt, polyoxyethylene encircle phenyl ether sulfonate (NH for example more ₄, Na), lauroleate, Voranol EP 2001 sulfonate and oleate.Wherein, Sodium docusate salt and polyoxyethylene vinylbenzene phenyl ether sulfonic acid NH ₄Salt is especially preferred.

The example of the nonionic surface active agent of HLB value 10 to 20 comprises that Voranol EP 2001, polyoxyalkylene alkyl, polyoxyethylene encircle phenyl ether, Sorbitol Powder fatty ester, polyoxyethylene sorbitol fatty ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine, polyoxyethylene alkylamide and alkyne diol more.Wherein, especially preferred polyoxyethylene lauryl ether, polyoxyethylene betanaphthyl ether, polyoxyethylene sorbitol monoleate and polyoxyethylene vinylbenzene phenyl ether.

Pigment dispersion among the present invention can be by following technology manufacturing: device, the ball formula of using as be used for the homogenizer of high-speed stirring disperse kneader such as ball mill and ball mill, shearing to disperse kneader such as roller mill and ultrasonic dispersing machine, be dissolved in aqueous medium with after preparing solution at dispersion agent, add organic or composite pigment and fully wetting to it, add this polymeric dispersant then.Mix and dispersion process after, have coarse particles through being everlasting in dispersions obtained, so need be obstructed to prevent production line with the coarse particles that strainer or centrifuge separator are removed the above diameter of 1 μ m usually.

Based on the pigment of 100 mass parts, the amount of dispersion agent is preferably 1 to 100 mass parts, more preferably 10 to 50 mass parts.When the quantity not sufficient of dispersion agent, pigment may not can micronization fully, and measure when excessive when this, the excessive dispersion agent that is not adsorbed onto on the pigment is easy to influence ink performance, causes the image ink bleed, perhaps water tolerance and/or scratch resistance deterioration.

Can show the colo(u)rant dispersion stability of the excellence under prolonged storage according to pigment dispersion of the present invention, therefore can be advantageously used for tinting material in the various application etc., the tinting material of the ink-jet recording ink of especially following explanation.

Recording ink

The recording ink of first embodiment

Recording ink according to first embodiment of the invention comprises according to the pigment dispersion, tensio-active agent, water-dispersed resin, wetting agent, the He Shui that invent, and also comprises other optional component such as penetrant, pH regulator agent etc. as required.

In recording ink, the median size D of pigment dispersion tinting material of the present invention ₅₀Be preferably and be not more than 150nm, more preferably be not more than 100nm.As median size D ₅₀When being higher than 150nm, the remarkable variation of jetting stability meeting may cause spray nozzle clogging or ink jet to depart from.As median size D ₅₀When being not more than 100nm, can promoting jetting stability and can improve color saturation.

In solid content, the amount of pigment dispersion is preferably 2 to 15 quality % in the recording ink, more preferably 3 to 10 quality %.When this amount was lower than 2 quality %, the color emissivity of printing ink and image density can significantly reduce, and when this amount was higher than 15 quality %, ink viscosity can excessively raise with the deterioration injection conditions, and production cost also can raise.

The recording ink of the second and the 3rd embodiment

The recording ink of the second or the 3rd embodiment comprises water dispersible tinting material, water-dispersed resin, wetting agent, He Shui at least according to the present invention, and comprises other optional component such as tensio-active agent, penetrant etc. as required.

In the recording ink of second embodiment, this water dispersible tinting material is the pigment dispersion that contains pigment, pigment dispersing agent and polymeric dispersion stabilizer; In the recording ink of the 3rd embodiment, this water dispersible tinting material is the pigment dispersion that contains from dispersed color and polymeric dispersion stabilizer.

In recording ink according to the present invention, scope can improve crystallized ability and improve color emissivity in the ratio of 2 to 8 A/B, and wherein A is the solid content of water-dispersed resin in this recording ink and the B solid content for this pigment in this water dispersible tinting material in this recording ink.Crystallized ability and color emissivity can be elevated to for example three or four times and be improved of pigment solid content along with the solid content of water-dispersed resin, and the effect that improves image density is tending towards saturated approximately greater than octuple the time, so scope sees it also is preferred in 2 to 8 A/B ratio originally from producing.Based on the gross weight of recording ink, the total content of water dispersible tinting material and water-dispersed resin is preferably 12 to 40 quality %, more preferably 15 to 35 quality %.When this content was lower than 12 quality %, the drying power on paper surface was understood variation, might cause the degradation of character picture on the common paper, and when this content was higher than 40 quality %, printing ink can be easy in the nozzle face drying, might cause the injection of difference.

The solid content of tinting material and water-dispersed resin can be by toner or water-dispersed resin are measured apart separately from printing ink.As under the situation of tinting material, the ratio of tinting material and water-dispersed resin can be measured weight loss by thermogravimetric analysis and determine at pigment.Under the situation that the molecular structure of tinting material is determined, the solid content of tinting material can pass through NMR, fluorescent X-ray analysis etc. and determine.The water dispersible tinting material

The water dispersible tinting material of second embodiment is the pigment dispersion that contains pigment, pigment dispersing agent and polymeric dispersion stabilizer.

The water dispersible tinting material of the 3rd embodiment is the pigment dispersion that contains pigment and polymeric dispersion stabilizer, wherein this pigment has hydrophilic radical from the teeth outwards at least, and is water dispersible and/or water miscible from dispersed color not having under the situation of dispersion agent.

Polymeric dispersion stabilizer can be by at least a mixture in a kind of or at least a this alpha-olefin/copolymer-maleic anhydride in the alpha-olefin/copolymer-maleic anhydride of following formula (1) expression and styrene/acrylic analog copolymer, water soluble polyurethane resin and the Polyester Resin Water Soluble.

Formula (1)

In formula (1), R represents alkyl, and the carbonatoms of this alkyl is preferably 6 to 25, more preferably 6 to 22; N is 30 to 100 integer.

Alpha-olefin/copolymer-maleic anhydride by formula (1) expression can suitably synthesize or buy from market; The example comprises T-YP112, T-YP114, T-YP115 and T-YP116 (Seico PMC Co. system).

This water soluble polyurethane resin can be commercially available those; The example comprises (Mitsui Takeda Chemical Co. systems) such as Takelac W-5025, Takelac W-6010, Takelac W-5661.

Polyester Resin Water Soluble can be commercially available those; The example comprise Nichigo polyester W-0030, Nichigo polyester W-0005S30WO, Nichigo polyester WR-961 (Nippon SyntheticChemical Industries, Co.), Pesresin A-210, Pesresin A 520 (Takamatsu Yusi Co.) etc.

At least a (B) at least a alpha-olefin/copolymer-maleic anhydride (A) and styrene/acrylic analog copolymer, water soluble polyurethane resin and Polyester Resin Water Soluble when mixing, blending ratio (A: B) be preferably 10: 90 to 90: 10

Based on the pigment of 100 mass parts, the solid content of polymeric dispersion stabilizer is preferably 1 to 100 mass parts, more preferably 5 to 50 mass parts.When this solid content was lower than 1 mass parts, the effect of stabilising dispersions can be ignored, and when greater than 100 mass parts, and ink jet can be obstructed and/or cost can be higher because of higher viscosity.

Pigment

Pigment can be for organic or inorganic.Pigment can contain dyestuff to regulate tone as long as weather resistance is kept.

The example of mineral dye comprises titanium oxide, ferric oxide, lime carbonate, barium sulfate, aluminium hydroxide, baryta yellow, cadmium red, chrome yellow and carbon black; Wherein, carbon black etc. is preferred.Carbon black can be those that made by known method such as contact process, oven process and pyrolysis method.

Pigment dyestuff comprises azo pigment, encircles pigment more, dyestuff inner complex, nitropigments, nitroso pigments and nigrosine.Wherein, azo pigment and many ring pigment are preferred.The example of azo pigment comprises azo lake, insoluble azo colour, condenses azo pigment and inner complex azo pigment.Many ring pigment comprise phthalocyanine pigment, perylene dye, perylene ketone pigment, anthraquinone pigment, quinacridone pigment, triazine dioxin pigment, indigoid pigment, thioindigo color, iso-dihydro-indole pigment and quinophthalones pigment.The example of dyestuff inner complex comprises basic dyestuff inner complex and matching stain inner complex.

The color of tinting material can suitably be selected according to purpose; For example, color can be achromatic or chromatic.Tinting material can be used alone or in combination of two or more.

The example of achromatic colour agent comprises that carbon black (C.I. Pigment black 7) is as furnace black, dim, acetylene black and channel black; Metal oxide such as cupric oxide, ferric oxide (C.I. Pigment black 11) and titanium oxide; Pigment dyestuff such as nigrosine (C.I. Pigment black 1).

The example of colour colouring pigment comprises C.I. Pigment Yellow 73 1,3,12,13,14,17,24,34,35,37,42 (iron oxide yellow), 53,55,74,81,83,95,97,98,100,101,104,408,109,110,117,120,128,138,150,151,153,183; C.I. pigment orange 5,13,16,17,36,43,51; C.I. Pigment red 1,2,3,5,17,22,23,31,38,48:2,48:2 (permanent bordeaux 2B (Ca)), 48:3,48:4,49:1,52:2,53:1,57:1 (brilliant carmine 6B), 60:1,63:1,63:2,64:1,81,83,88,101 (colcother), 104,105,106,108 (cadmium reds), 112,114,122 (quinacridone magenta), 123,146,149,166,168,170,172,177,178,179,185,190,193,209,219; C.I. pigment violet (rhodamine color lake), 3,5:1,16,19,23,38; C.I. pigment blue 1,2,15 (phthalocyanine blue) 15:1,15:2,15:3 (phthalocyanine blue), 16,17:1,56,60,63; C.I Pigment green 1,4,7,8,10,17,18,36.

Be used for the 3rd embodiment recording ink be that surface modification is to have at least hydrophilic radical directly or by other atomic radical to be bonded to those of surface of pigments from dispersed color.Surface treatment can be carried out in the following manner: particular functional group such as sulfo group and carboxyl are chemically bonded to the surface of pigment, or carry out wet oxidation with hypohalous acid (hypohalous acid) or its salt pair pigment.Especially preferred is that carboxyl is bonded to its surperficial water dispersible pigment.This surface treatment of carrying out with carboxyl can improve dispersion stabilization, high-quality printing is provided and improves the water tolerance of record thing after printing.

In addition, even this printing ink also can show excellent redispersibility after drying, therefore even long-term idle and also spray nozzle clogging can not occur basically after the moisture in the printing ink around the ink gun nozzle has evaporated thus, it just can carry out suitable printing again in the simple back of cleaning.

Preferably, in printing ink, should be 0.01 to 0.16 μ m from the equal particle diameter of the body of dispersed color.

Preferably, should show ionic nature, more preferably, have positively charged ion or anionic charge from disperse black carbon.

The example of this anionic hydrophilic group comprises-COOM ,-SO ₃M ,-PO ₃HM ,-PO ₃M ₂,-SO ₂NH ₂, and-SO ₂NHCOR, wherein M represents that a kind of in hydrogen atom, basic metal, ammonium and the organic ammonium, R represent that carbonatoms is 1 to 12 alkyl, can be substituted the phenyl that base replaces and can be substituted a kind of in the naphthyl that base replaces.Wherein, preferably surface bond-COOM or-SO ₃The coloured pigment of M.

Basic metal M in the hydrophilic radical comprises, for example, and lithium, sodium and potassium.The example of organic ammonium comprises list or trimethyl ammonium, list or triethyl ammonium, list or three methanol ammonium hydroxides etc.For the method for the coloured pigment that produces the band anionic charge, can be in the following manner will-surface of COONa introducing coloured pigment on, for example, handle coloured pigment, sulfonation or react with diazonium salt with hypochlorite oxidation.

The cationic hydrophilic group is preferably quaternary ammonium group, quaternary ammonium group more preferably as follows.The carbon black that one of is connected with in these groups at least is the preferred tinting material of the present invention.

-NH ₃ ⁺、-NR ₃ ⁺、

Bonding the positively charged ion of hydrophilic radical can be from disperse black carbon according to using suitably preparation; For example, by handling and N-ethyl pyridinyl as follows can be connected to carbon black with bromination 3-amino-N-ethylpyridine.

This hydrophilic radical can be connected to the sooty surface by other atomic radical.Described other atomic radical can be 1 to 12 alkyl for carbonatoms, can be substituted the phenyl that base replaces and can be substituted the naphthyl that base replaces.Being connected to the hydrophilic radical of carbon blacksurface and the specific examples of other atomic radical has-C ₂H ₄COOM (M: one of basic metal and quaternary ammonium) ,-PhSO ₃M (Ph: phenyl, M: one of basic metal and quaternary ammonium) and-C ₅H ₁₀NH ₃ ⁺

Conventional pigment dyestuff or inorganic pigment granules can be with pigment dyestuff or carbon black coated with the preparation composite pigments, and can be used for the present invention suitably.Prepare these composite pigments method can for, for example, pigment dyestuff is deposited on the inorganic pigment granules, or by the mechanically mixing and the mechanochemistry technology of grinding organic and mineral dye.As required, can be arranged between organic and the mineral dye to strengthen bounding force therebetween by polysiloxane and alkyl silane synthetic organic silane compound layer.

The example of pigment dyestuff comprises: as the nigrosine of achromatic pigment; Anthraquinone, phthalocyanine blue, phthalocyanine green, diazonium, monoazo, pyranthrone, perylene, heterocyclic yellows, quinacridone, (sulphur) indigo as coloured pigment.Wherein, from the color development ability, carbon black, phthalocyanine pigment, quinacridone pigment, monoazo yellow pigment, disazo yellow pigment and heterocyclic yellow pigments are particularly preferred.

3,15:4), aluminium phthalocyanine etc. the example of phthalocyanine blue comprises copper phthalocyanine blue and derivative thereof (CI. pigment Blue 15:.The example of quinacridone pigment comprises C.I. pigment orange 48, C.I. pigment orange 49, C.I. pigment red 122, C.I. Pigment red 192, C.I. Pigment red 202, C.I. Pigment red 206, C.I. Pigment Red 207, C.I. Pigment red 209, C.I. pigment violet 19, C.I. pigment violet 42 etc.The example of monoazo yellow pigment comprises C.I. Pigment Yellow 73 74, C.I. Pigment Yellow 73 109, C.I. pigment Yellow 12 8, C.I. Pigment Yellow 73 151 etc.The example of disazo yellow pigment comprises C.I. pigment Yellow 14, C.I. Pigment Yellow 73 16, C.I. pigment yellow 17 etc.The example of heterocyclic yellow pigments comprises C.I. Pigment Yellow 73 117, C.I. pigment yellow 13 8 etc.Other tinting pigment can be referring to " color index (The Color Index), the third edition, dyer's dyer association (1982) ".

Mineral dye can be enumerated titanium dioxide, silicon-dioxide, aluminum oxide, ferric oxide, ironic hydroxide and stannic oxide; Particle shape is preferably lower long-width ratio, most preferably is sphere.Under the situation of absorption colour colouring pigment, the color of mineral dye is preferably transparent or white, and its color can be black under the situation of absorption black colorant.The primary particle diameter of organic pigment particle is preferably and is not more than 100nm, more preferably 5 arrives 50nm.

Inorganic pigment granules with as pigment dyestuff or sooty mass ratio, the i.e. inorganic pigment granules of coloured material: tinting material is preferably 3: 1 to 1: 3, and more preferably 3: 2 to 1: 2.Under the lower situation of the mass ratio of tinting material, color development ability or tinctorial strength are poor, and under the mass ratio condition with higher of tinting material, transparency or tone can deteriorations.

The example of the coloring agent particle that inorganic pigment granules applies with pigment dyestuff or carbon black comprises the matrix material of TodaKogyo Corporation such as silicon-dioxide/carbon black composite material, silicon-dioxide/phthalocyanine C.I.PB15:3 matrix material, silicon-dioxide/dual-azo yellow matrix material, silicon-dioxide/quinacridone C.I.PR122 matrix material etc.; The primary particle diameter of these products is small enough to use.

When elementary particle diameter is the inorganic pigment granules of 20nm when applying with the pigment dyestuff of equivalent, the primary particle diameter strain of this pigment is about 25nm.When these pigment can be dispersed into their primary granule with suitable dispersion agent, can prepare and disperse particle diameter was the printing ink that is dispersed with superfine pigment of 25nm.In these composite pigments, not only lip-deep pigment dyestuff influences dispersion, and the performance of the mineral dye at center also embodies by the thick thin layer of 2.5nm, should be based on organic and mineral dye to the selection of pigment dispersing agent.

Pigment dispersing agent

Tinting material in second embodiment contains pigment dispersing agent.It is a kind of in 10 to 20 the nonionic surface active agent that this pigment dispersing agent is preferably anion surfactant and HLB value.

The specific examples of anion surfactant comprises Voranol EP 2001 acetic ester, alkylbenzene sulfonate (NH for example ₄, Na, Ca), alkyl diphenyl base ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate (NH for example ₄, Na, Ca), dialkyl succinate sodium sulfonate, naphthene sulfonic acid formalin condenses sodium salt, polyoxyethylene encircle phenyl ether sulfonate (NH for example more ₄, Na), lauroleate, Voranol EP 2001 sulfonate and oleate.Wherein, Sodium docusate salt and polyoxyethylene vinylbenzene phenyl ether sulfonic acid NH ₄Salt is especially preferred.

Based on the pigment of 100 mass parts, the amount of this dispersion agent is preferably 1 to 100 mass parts, more preferably 10 to 50 mass parts.When the quantity not sufficient of this dispersion agent, pigment may not can micronization fully, and measure when too high when this, the excessive dispersion agent that is not adsorbed onto on the pigment is easy to influence ink performance, causes the image ink bleed, perhaps water tolerance and/or scratch resistance deterioration.

Pigment dispersion can be by following technology manufacturing: device, the ball formula of using as be used for the homogenizer of high-speed stirring disperse kneader such as ball mill and ball mill, shearing to disperse kneader such as roller mill and ultrasonic dispersing machine, be dissolved in aqueous medium with after preparing solution at organic dispersing agent, add pigment and fully wetting to it, add this polymeric dispersant then.Mix and dispersion process after, have coarse particles through being everlasting in dispersions obtained, so need be obstructed to prevent production line with the coarse particles that strainer or centrifuge separator are removed the above diameter of 1 μ m usually.

In recording ink, the median size D of pigment dispersion ₅₀Be preferably and be not more than 150nm, more preferably be not more than 100nm.As median size D ₅₀When being higher than 150nm, the remarkable variation of jetting stability meeting might cause spray nozzle clogging or ink jet to depart from.As median size D ₅₀When being not more than 100nm, can promoting jetting stability and can improve color saturation.

In solid content, the amount of pigment dispersion is preferably 2 to 15 quality % in the whole recording ink, more preferably 3 to 12 quality %.When this amount was lower than 2 quality %, color emissivity and image density can significantly reduce, and when this amount was higher than 15 quality %, ink viscosity can excessively raise with the deterioration injection conditions, and production cost also can raise.

The total composition of the recording ink of first to the 3rd embodiment

Tensio-active agent

Preferably, tensio-active agent is a kind of in organic silicon surfactant and the fluorochemical surfactant, condition be this tensio-active agent preferably cause lower surface tension and higher homogenizing ability and with other tinting material or wetting agent bonded situation under do not reduce dispersion stabilization; Especially, preferred fluorochemical surfactant.

Preferably this fluorochemical surfactant per molecule contains 2 to 16 carbon atoms with the fluorine atom bonding, more preferably 4 to 16 carbon atoms.Be less than at the carbon atom of fluorine atom institute bonding under 2 the situation, the effect of fluorine atom can be ignored, and under more than 16 situation, the printing ink storage stability can reduce.

The example of fluorochemical surfactant comprises perfluoro alkyl sulfonic acid compound, perfluoro carboxylic acid compound, perfluoralkyl phosphate compound, perfluoroalkyl ethylene oxide adduct and have the polyoxyalkylene ether polymer compound of perfluoroalkyl ether group in its side chain.Wherein, from lower one-tenth bubble performance, the polyoxyalkylene ether polymer compound that has the perfluoroalkyl ether group in its side chain is especially preferred.

The perfluoro alkyl sulfonic acid examples for compounds comprises: perfluoro alkyl sulfonic acid and fluorinated alkyl sulfonate; The perfluoro carboxylic acid examples for compounds comprises perfluoro carboxylic acid and perfluoroalkyl carboxylate.

The perfluoralkyl phosphate compound comprises, for example, and perfluoralkyl phosphate and perfluoralkyl phosphate salt.

The polyoxyalkylene ether polymer examples for compounds that has the perfluoroalkyl ether group in its side chain comprises: in side chain, have the perfluoroalkyl ether group the polyoxyalkylene ether polymer, in side chain, have the perfluoroalkyl ester group the polyoxyalkylene ether polymer sulfuric acid and in side chain, have the salt of the polyoxyalkylene ether polymer of perfluoroalkyl ether group.

The gegenion of salt comprises Li, Na, K, NH in these fluorochemical surfactants ₄, NH ₃CH ₂CH ₂OH, NH ₂(CH ₂CH ₂OH) ₂And NH (CH ₂CH ₂OH) ₃

Fluorochemical surfactant can synthesize or buy from market suitably.

The example of commercially available fluorochemical surfactant comprises: Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (Asahi Glass Co., Ltd. make), Fullard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (Sumitomo 3M Ltd. system), Megafac F-470, F1405, F-474 (Dainippon Ink And Chemicals, Inc. system), Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (DuPont system), FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (Neos Co. system) and PF-151N (Omnova Inc. system).Wherein, from suitable print quality, especially color emissivity on paper and tinctorial property uniformly, FT-110, FT-250, FT-251, FT 400S, FT-150, FT-400SW (Neos Co. system) and PF-151N (Omnova Inc. system) are especially preferred.

The specific examples of fluorochemical surfactant is those that are expressed from the next.

(1) anionic fluorosurfactants

In following formula, Rf represents the mixing of the fluorine-containing hydrophobic grouping that is expressed from the next; A represents-SO ₃X ,-COOX or-PO ₃(X is a pair anion to X, is hydrogen atom, Li, Na, K, NH specifically ₄, NH ₃CH ₂CH ₂OH, NH ₂(CH ₂CH ₂OH) ₂, or NH (CH ₂CH ₂OH) ₃).

In following formula, the fluoro-containing group of Rf ' for being expressed from the next; X is same as described above basically, and n represents 1 or 2 integer, and m represents 2-n.

In following formula, n represents 3 to 10 integer.

Rf’-S-CH ₂CH ₂-COO·X

In following formula, Rf ' and X are same as described above basically.

Rf’-SO ₃·X

In following formula, Rf ' and X are same as described above basically.

(2) non-ionic type fluorochemical surfactant

In following formula, Rf is same as described above basically, and n represents 5 to 20 integer.

In following formula, Rf ' is same as described above, and n represents 1 to 40 integer.

(3) amphoteric fluorotensides

In following formula, Rf is same as described above basically.

(4) oligomeric fluorochemical surfactant

In following formula, the fluoro-containing group that Rf ' expression is expressed from the next, wherein l represents that 0 to 10 integer and X are same as described above basically.

In following formula, n is 1 to 4 integer.

In following formula, Rf " same as described above basically; L, m and n represent 0 to 10 integer separately.

Organic silicon surfactant can be selected suitably according to purpose, is preferably those that are difficult to degrade under higher pH; The example comprises: have polydimethylsiloxane, two terminal-modified polydimethylsiloxanes, terminal-modified polydimethylsiloxanes of modification side chain and have the modification side chain and two terminal-modified polydimethylsiloxanes.From the suitable performance as aqueous tenside, the modification group is preferably polyoxyethylene group, polyoxyethylene polyoxypropylene group etc.

These tensio-active agents can synthesize or buy from market suitably; The example is available from those of BYKChemie GmbH, Shin-Etsu Silicones Co.Ltd., Dow Corning Tray Co.Ltd etc.

Polyether-modified organic silicon surfactant can be selected according to using suitably, for example, the compound that can represent for following formula, wherein polyalkylene oxide units is introduced the Si side chain of dimethyl polysiloxane.

X＝-R(C ₂H ₄O)a(C ₃H ₆O)bR′

In following formula, m, n, a and b represent integer separately; R and R ' represent alkyl or alkylidene group separately.

Polyether-modified organic silicon surfactant can be buied from market; The example comprises KF-618, KF-642 and KF 643 (Shin-Etsu Chemical Co. system).

Except above-mentioned fluorochemical surfactant and organic silicon surfactant, can also use anion surfactant, nonionic surface active agent and amphoterics as required.

The example of anion surfactant comprises Voranol EP 2001 acetate, dodecylbenzene sulfonate, sulphosuccinates, lauroleate and polyoxyethylene alkyl ether sulfate salt.

The example of nonionic surface active agent comprises alkyne diol tensio-active agent, Voranol EP 2001, polyoxyethylene alkyl phenyl ether, polyxyethylated ester and polyoxyethylene sorbitol fatty acid ester.

The specific examples of above-mentioned alkyne diol tensio-active agent comprises 2,4,7,9-tetramethyl--5-decine-4, and 7-glycol, 3,6-dimethyl-4-octyne-3,6-two is pure and mild 3,5-dimethyl-1-hexin-3-alcohol.The alkyne diol tensio-active agent can be buied from market, for example, and the Surfynol 104,82,465,485 of supply and TG (AirProducts Co. system, the U.S.)

The specific examples of above-mentioned amphoterics comprises lauryl aminopropionate, lauryl dimethyl trimethyl-glycine, stearyl dimethyl betaine, lauryl dihydroxy ethyl trimethyl-glycine, lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, stearyl dimethyl amine oxide, dihydroxy ethyl lauryl amine oxide, polyoxyethylene plam oil alkyl dimethyl amine oxide, dimethyl alkyl (palm) trimethyl-glycine and dimethyl lauryl betaine.

These tensio-active agents can for, for example, the commercially available prod of Nikko Chemicals Co.Ltd., NipponEmulsion Co.Ltd., Nippon Shokubai Co.Ltd., Toho Chemical Industry Co.Ltd., Kao Corporation, Adeka Co.Ltd., Lion Corporation, Aoki Oil IndustrialCo.Ltd. and Sanyo Chemical Industries Ltd.

Above-mentioned tensio-active agent can be used alone or in combination.Have certain situation, wherein tensio-active agent is insoluble in printing ink but easily dissolves with other printing ink, gained solution through the time stable.

The content of tensio-active agent is preferably 0.01 to 3.0 quality %, more preferably 0.5 to 2.0 quality %.When this content during, add the effect of tensio-active agent and can ignore, and when this content during greater than 3.0 quality %, image density can reduce and/or understand because of print through is appearred in the too high perviousness of recording medium less than 0.01 quality %.

Water-dispersed resin

Water-dispersed resin can according to purpose from, for example, suitably select in condensation synthetic resins, addition synthetic resins and the natural polymeric compounds.

The example of condensation synthetic resins comprises vibrin, urethane resin, poly epoxy resin, polyamide resin, polyether resin and silicone resin.The example of addition synthetic resins comprises polyolefin resin, polystyrene resin, polyvinyl alcohol resin, polyvinylesters resin, polyacrylic acid resinoid and unsaturated carboxylic acid resin.The example of natural polymeric compounds comprises Mierocrystalline cellulose, rosin and natural rubber.

Water-dispersed resin can use with the form of homopolymer or multipolymer, and can be selected from unipolar type, core-shell-type or automatic feed type (power feed-type) emulsion.

Water-dispersed resin can be that resin itself has hydrophilic radical and is self-dispersed resin, or resin itself does not have dispersiveness but given dispersed resin by tensio-active agent or resin with hydrophilic radical.Wherein, the ionomer of vibrin and urethane resin, and the emulsion of the resin particle that emulsion/suspension polymerization obtained by unsaturated monomer is preferred.Under the situation of letex polymerization unsaturated monomer, can be easy to obtain water-dispersed resin, because this resin emulsion is to obtain by reaction in the water that has added unsaturated monomer, polymerization starter, tensio-active agent, chain-transfer agent, sequestrant and pH regulator agent, and can be easy to obtain destination properties, be easy to change because this resin constitutes.

The example of unsaturated monomer comprises unsaturated carboxylic acid, (methyl) acrylate monomer, (methyl) acrylic acid amides monomer, aromatic vinyl monomer, vinyl cyanide based compound monomer, vinyl monomer, allylic cpd monomer, olefinic monomer, diene monomers, contains the oligopolymer of unsaturated carbon.These can be used alone or in combination of two or more.These monomeric combinations make might improve various performances neatly, for example, uses the polyreaction of oligopolymer polymerization starter or the improvement that graft reaction can cause resin property.

The example of unsaturated carboxylic acid comprises: vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid and toxilic acid.

The example of simple function (methyl) acrylate comprises methyl methacrylate, Jia Jibingxisuanyizhi, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid n-pentyl ester, the methacrylic isoamyl valerate, the just own ester of methacrylic acid, methacrylic acid 2-ethylhexyl, Octyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, the methacrylic acid stearyl, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, dimethylaminoethyl methacrylate, the methacryloxyethyl leptodactyline, the 3-methacryloxypropyl trimethoxy silane, methyl acrylate, ethyl propenoate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, the vinylformic acid n-pentyl ester, the vinylformic acid isopentyl ester, the just own ester of vinylformic acid, 2-EHA, Octyl acrylate, decyl acrylate, dodecylacrylate, the vinylformic acid stearyl, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, glycidyl acrylate, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, vinylformic acid dimethylamino ethyl ester and acryloxy ethyl-trimethyl ammonium salt.

The example of multifunctional (methyl) acrylate comprises Ethylene glycol dimethacrylate, dimethacrylate glycol ether ester, the dimethacrylate triethyleneglycol ester, the dimethacrylate macrogol ester, dimethacrylate 1, the 3-butanediol ester, dimethacrylate 1, the 4-butanediol ester, dimethacrylate 1,6-hexylene glycol ester, the dimethacrylate DOPCP, dimethacrylate dipropylene glycol ester, dimethacrylate polypropylene glycol ester, dimethacrylate polytetramethylene glycol ester, 2,2 '-two (4-methacryloxy diethoxy phenyl) propane, trimethylolpropane trimethacrylate, the trimethylolethane trimethacrylate methacrylic ester, the diacrylate macrogol ester, the diacrylate triethyleneglycol ester, diacrylate 1, the 3-butanediol ester, diacrylate 1, the 4-butanediol ester, diacrylate 1,6-hexylene glycol ester, diacrylic acid pentyl diol ester, diacrylate 1,9-nonanediol ester, diacrylate polypropylene glycol ester, 2,2 '-two (4-acryloxy propoxy-phenyl) propane, 2,2 '-two (4-acryloxy diethoxy phenyl) propane, Viscoat 295, the trimethylolethane trimethacrylate acrylate, the tetramethylol methane triacrylate, the two trishydroxymethyl esters of tetrapropylene acid, the tetramethylol methane tetraacrylate, pentaerythritol tetracrylate and six vinylformic acid dipentaerythritol ester.

The monomeric example of (methyl) acrylic acid amides comprises acrylamide, Methacrylamide, N,N-DMAA, methylene diacrylamine and 2-acrylamide-2-methyl propane sulfonic acid ester.

The example of aromatic vinyl monomer comprises vinylbenzene, alpha-methyl styrene, Vinyl toluene, 4-t-butyl styrene, chloro-styrene, vinyl benzene methyl ether, vinyl naphthalene and Vinylstyrene.

The monomeric example of vinyl cyano group comprises vinyl cyanide and methacrylonitrile.

The example of allyl monomer comprises allyl sulphonic acid and salt, allyl amine, chlorallylene, diallyl amine and diallyl dimethyl ammonium salt; The example of olefinic monomer comprises ethene and propylene; The example of diene monomers comprises divinyl and chlorine pentadiene.

The example of vinyl monomer comprises vinyl-acetic ester, vinylidene chloride, vinylchlorid, vinyl ether, vinyl ketone, vinyl pyrrolidone, vinyl sulfonic acid and salt thereof, vinyltrimethoxy silane and vinyltriethoxysilane.

The example that contains the oligopolymer of unsaturated carbon comprises: have methacryloyl styrene oligomer, have methacryloyl the styrene-acrylonitrile oligopolymer, have methacryloyl the methyl methacrylate oligopolymer, have the dimethyl siloxane oligopolymer of methacryloyl and have the polyester oligomer of acryl.

For water-dispersed resin, molecular chain might rupture by dispersion destruction or hydrolysis under strong basicity or acidic conditions.Therefore, its pH value is preferably 4 to 12, and is preferred 6 to 11, and more preferably 7 to 9, particularly from the compatibility of water dispersible tinting material.

The median size D of water-dispersed resin ₅₀Relevant with the viscosity of dispersion liquid; That is to say that when composition was identical with solid content, particle diameter was more little, viscosity is high approximately.Therefore, become too high, the median size D of water-dispersed resin in order to prevent ink viscosity ₅₀Be preferably more than the 50nm.On the other hand, greatly to tens microns situation, granularity hinders greater than the nozzle bore of ink gun and uses at particle diameter, even macrobead also is easy to damage jetting stability when perhaps diameter is less than nozzle bore.Therefore, median size D ₅₀Be preferably and be not more than 200nm, more preferably be not more than 150nm.

Water-dispersed resin is fixed to the water dispersible tinting material on the paper surface, and preferably becomes film at ambient temperature, thereby improves the fixed performance of tinting material.Therefore, the minimum film-forming temperature of water-dispersed resin (MFT) is below 30 ℃, more preferably below 20 ℃.

In addition, under the second-order transition temperature of water-dispersed resin was situation below-40 ℃, resin molding is easy to toughness and printed matter may be clamminess, and therefore, the second-order transition temperature of this water-dispersed resin is preferably more than-30 ℃.

In solid content, the content of water-dispersed resin in recording ink is preferably 4 to 30 quality %, more preferably 6 to 24 quality %.

Wetting agent

Recording ink according to the present invention comprises the water as liquid medium, comprises also that therefore wetting agent is to prevent ink setting and to improve dispersion stability.Wetting agent can provide the advantageous effects of the relatively poor injection that improves solubleness and prevent to cause because of the water evaporation.

Wetting agent can be selected according to using suitably; The example comprises polyvalent alcohol, polyol alkyl ether, polyvalent alcohol aryl ethers, nitrogenous heterogeneous ring compound, acid amides, amine, sulfocompound, propylene carbonate, NSC 11801 etc.These can be used alone or in combination.

Examples of polyhydric alcohols comprises glycerine, glycol ether, 1,3-butyleneglycol, 3-methyl isophthalic acid, 3-butyleneglycol, triglycol, propylene glycol, dipropylene glycol, TriMethylolPropane(TMP), trimethylolethane, ethylene glycol, tripropylene glycol, Tetraglycol 99, hexylene glycol, polyoxyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexylene glycol, glycerol, 1,2,6-hexanetriol, 1,2,4-trihydroxybutane, 1,2,3-trihydroxybutane, penta triol etc.

The example of polyol alkyl ether comprises ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diglycol monotertiary methyl ether, carbiphene, diglycol monotertiary butyl ether, Tetraglycol 99 monomethyl ether, propylene glycol list ethyl ether etc.The example of polyvalent alcohol aryl ethers comprises glycol monomethyl phenyl ether, glycol monomethyl benzylic ether etc.

The example of nitrogen-containing heterocycle compound comprises 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, N-hydroxyethyl-2-Pyrrolidone, 1,3-methylimidazole diketone, ε-Ji Neixianan, gamma-butyrolactone etc.

The example of acid amides comprises methane amide, N-methylformamide, N, dinethylformamide etc.

The example of amine comprises monoethanolamine, diethanolamine, trolamine, mono aminoethane, diethylamine, triethylamine etc.The example of sulfocompound comprises dimethyl sulfoxide (DMSO), tetramethylene sulfone, thiodiethanol etc.

Other wetting agents be preferably sacchariferous those; The example of described sugar comprises monose, disaccharides, oligose (comprising trisaccharide and tetrose) and polysaccharide.Specific examples comprises glucose, seminose, fructose, ribose, wood sugar, pectinose, semi-lactosi, maltose, cellobiose, lactose, sucrose, trehalose and trisaccharide maltose etc.Polysaccharide is a sugar in this generalized definition, and it contains the material that is present in widely in the nature, as alpha-cylodextrin and Mierocrystalline cellulose.The reducing sugar that these sugared derivatives comprise above-mentioned sugar is as by general formula: HOCH ₂(CHOH) _nCH ₂The sugar alcohol that OH represents, the wherein integer of " n " expression 2 to 5; Carbohydrate such as glyconic acid, uronic acid; Amino acid, thionic acid etc.Wherein, sugar alcohol is preferred, and its specific examples comprises maltose alcohol and Sorbitol Powder.

In these wetting agents, from storage and discharge stability, special preferably glycerine, glycol ether, 1,3 butylene glycol, 3-methyl isophthalic acid, 3-butyleneglycol, triglycol, 1,6-hexylene glycol, propylene glycol, 1,5-pentanediol, dipropylene glycol and TriMethylolPropane(TMP).

The mass ratio of pigment and wetting agent influences the stability that printing ink is discharged from ink head significantly.When the amount of wetting agent was compared deficiency with the pigment solid content, near the water evaporation the printing ink meniscus of nozzle can cause discharging fault.

The content of wetting agent in recording ink is preferably 10 to 50 quality %, more preferably 15 to 35 quality %, more preferably 22.5 to 32.5 quality %.Recording ink in this scope can advantageously provide drying, storage and reliability.When this content during less than 10 quality %, printing ink is easy in nozzle face rapid drying, and this may cause relatively poor injection, and when this content during greater than 50 quality %, the rate of drying on paper surface is lower simultaneously, and this also can damage the print quality of character on the common paper.

Penetrant

Penetrant is preferably and contains polyol compound at least, and its solubleness in water under 20 ℃ is 0.2 to 5.0 quality %.The example of polyol compound comprises aliphatic diol such as 2-ethyl-2-methyl isophthalic acid, ammediol, 3,3-dimethyl-1,2-butyleneglycol, 2,2-diethyl-1, ammediol, 2-methyl-2-propyl group-1, ammediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexylene glycol, 5-hexene-1,2-two pure and mild 2-ethyls-1, the 3-hexylene glycol.Wherein, 2-ethyl-1,3-hexylene glycol and 2,2,4-trimethylammonium-1, the 3-pentanediol is especially preferred.

Other penetrants that are suitable for using simultaneously can suitably be selected, as long as can regulate the physicals that needs; The example comprises alkyl or allyl ethers such as diglycol monotertiary phenyl ether, glycol monomethyl phenyl ether, ethylene glycol monoallyl ether, diglycol monotertiary phenyl ether, diglycol monotertiary butyl ether, propylene glycol single-butyl ether and the Tetraglycol 99 chloro-phenyl-ether of polyvalent alcohol; With lower alcohol such as ethanol.

The content of penetrant in printing ink is preferably 0.1 quality % to 4.0 quality %.When this content during less than 0.1 quality %, rate of drying can reduce, therefore may cause the image ink bleed, and when this content during greater than 4.0 quality %, the dispersion stabilization meeting variation of tinting material, spray nozzle clogging is tending towards easily taking place, and image density is tending towards reducing or print through takes place owing to the too high perviousness of recording medium is tending towards.

The pH regulator agent

The pH regulator agent can suitably be selected, only otherwise recording ink is caused disadvantageous effect and can be with pH regulator to 7 to 11; The example comprises hydramine, alkali metal hydroxide, ammonium hydroxide, phosphonium hydroxides and alkaline carbonate.Under pH surpassed 11 situation, the material of ink gun and/or printing ink feeding unit can dissolve, and such fault can take place, as printing ink deterioration or leakage, relatively poor ink jet etc.

The example of hydramine comprises: diethanolamine, trolamine and 2-amino-2-ethyl-1, ammediol; The example of alkali metal hydroxide comprises lithium hydroxide, sodium hydroxide and potassium hydroxide.

The example of ammonium hydroxide comprises: ammonium hydroxide, quaternary ammonium hydroxide and quaternary phosphonium hydroxide; The example of alkaline carbonate comprises Quilonum Retard, yellow soda ash and salt of wormwood.

Other compositions can be selected suitably according to purpose, and comprise, for example, and antiseptic-germicide/anti-mycotic agent, sequestrant, rust-preventive agent, antioxidant, UV light absorber, oxygen absorbent and photostabilizer.

The example of antiseptic-germicide/anti-mycotic agent comprises Sodium dehydroacetate, sodium sorbate, 2-pyridine sulfydryl-1-sodium oxide, Sodium Benzoate and sodium pentachlorophenol.

The example of sequestrant comprises sodium ethylene diamine tetracetate, B,EDTA, Oxyethylethylenediaminetriacetic acid sodium, diethylene triaminepentaacetic acid(DTPA) sodium and uramildiacetic acid sodium.

The example of rust-preventive agent comprises: bisul-phite, Sulfothiorine, sulfo-diglycollic acid ammonium, di-isopropyl ammonium nitrate, four pentaerythritol tetranitrates, dicyclohexyl ammonium nitrate and benzotriazole.

The example of antioxidant comprises phenolic antioxidant (comprising hindered phenol antioxidant), amine antioxidant, sulphur antioxidant and phosphorus antioxidant.

The example of phenolic antioxidant (comprising hindered phenol antioxidant) comprises butylated hydroxyanisol, 2,6-di-t-butyl-4-ethylphenol, β-(3,5-di-t-butyl-hydroxy phenyl) propionic acid stearyl ester, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 2,2 '-methylene radical-two (4-ethyls-6-tert.-butyl phenol), 4,4 '-butylidene-two (3 methy 6 tert butyl phenols), 3, two [1,1-dimethyl-2-[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] ethyls of 9-]-2,4,8,10-four spiral shells-[5.5] undecane, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene and four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] methane.

The example of amine antioxidant comprises phenyl-, Alpha-Naphthyl amine, N, N '-two sec-butyls-Ursol D, thiodiphenylamine, N, N '-diphenyl-para-phenylene diamine, 2, the 6-ditertbutylparacresol, 2, the 6-DI-tert-butylphenol compounds, 2,4-dimethyl-5-tert.-butyl phenol, butyl hydroxyanisole, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), four [methylene radical-3-(3,5-di-t-butyl-4-dihydroxy phenyl)-and propionic acid] methane and 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane.

The example of sulphur antioxidant comprises 3,3 '-Tyox B, distearylthiodi-propionate, dilauryl thiodipropionate stearyl ester, 3,3 '-thio-2 acid two myristins, β, β '-distearylthiodi-propionate, 2-mercaptobenzimidazole and dilauryl thioether.

The example of phosphorus antioxidant comprises triphenyl phosphite, phosphorous acid stearyl, triisodecyl phosphite ester, trilauryl trithiophosphite and trisnonyl phenyl phosphite.

The example of UV light absorber comprises benzophenone UV-absorber, benzotriazole UV absorbers, salicylate UV light absorber, cyanoacrylate UV light absorber and nickel complexing salt UV light absorber.

The example of benzophenone UV-absorber comprises: Octabenzone, 2-hydroxyl-4-positive 12-alkoxy benzophenone, 2,4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone and 2,2 ', 4,4 '-tetrahydroxybenzophenone.

The example of benzotriazole UV absorbers comprises: 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole and 2-(2 '-hydroxyl-3 '-tertiary butyl-5 '-aminomethyl phenyl)-the 5-chlorobenzotriazole.

The example of salicylate UV light absorber comprises: Whitfield's ointment phenylester, Whitfield's ointment to tert-butyl-phenyl ester and Whitfield's ointment to the octyl phenyl ester.

The example of cyanoacrylate UV light absorber comprise 2-cyano group-3,3 '-diphenyl-ethyl acrylate, 2-cyano group-3-methyl-3-(p-methoxyphenyl) methyl acrylate, 2-cyano group-3-methyl-3-(p-methoxyphenyl) butyl acrylate.

The example of nickel complexing salt UV light absorber comprises two (octyl phenyl) nickelous sulfides, 2,2 '-thiobis (uncle's 4-octyl group phthalic acid)-n-Butyl Amine 99 nickel (II), 2,2 '-thiobis (uncle's 4-octyl group phthalic acid)-2 ethyl hexylamine nickel (II) and 2,2 '-thiobis (uncle's 4-octyl group phthalic acid) trolamine nickel (II).

According to recording ink of the present invention can by will be according to pigment dispersion of the present invention, have at least organic silicon surface active agent or fluorochemical surfactant, water-dispersed resin, wetting agent and optional additional components to be dispersed or dissolved in the aqueous medium, and further stir as required and mix and prepare.Dispersion steps can utilize sand mill, homogenizer, ball mill, coating agitator or ultra-sonic dispersion agent to carry out, and can carry out with the conventional whipping device, magnetic stirrer or the high-speed dispersion equipment that are equipped with agitating vane and mix step.

The physicals of recording ink of the present invention can be selected according to using suitably; Preferred viscosities and surface tension are in following ranges.

The viscosity of recording ink of the present invention is preferably under 25 ℃ and is not more than 20mPas, more preferably is not more than 15mPas.When viscosity was higher than 20mPas, jetting stability may depend on the structure of head and be difficult to keep.

The surface tension of recording ink of the present invention is preferably under 25 ℃ and is not more than 35mN/m, more preferably is not more than 30mM/m.When surface tension was higher than 35mN/m, the printing ink homogenizing may be difficult to occur on recording medium and can prolong time of drying.

Color according to recording ink of the present invention can be selected suitably according to purpose, and can be yellow, magenta, cyan or black.The record that utilization combines the printing ink group of these two or more colors can form multicolor image; Utilize the record of panchromatic printing ink group can form full-colour image.

Can be applied to equip any basically printer of various ink guns suitably according to recording ink of the present invention, described ink gun for example, so-called piezo-electric type ink gun is wherein by changing volume in the printing ink stream with by making the oscillating plate distortion that forms printing ink stream wall spray ink droplet (referring to JP-A No.02-51734) as the printing ink in the effect extruding printing ink stream of the piezoelectric element of Pressure generator; So-called heat energy ink gun is wherein by utilizing the printing ink in the heating resistive element heating printing ink stream to produce bubble (referring to JP-A No.61-59911); Electrostatic inkjet head, wherein electrode is provided with relative position with the oscillating plate that forms printing ink stream wall, and makes stereomutation in the printing ink stream with ink jet (referring to JP-A No.06-71882) by the electrostatic force that produces between this electrode and oscillating plate.

Can be used for various article according to recording ink of the present invention, as fountain pen, ballpoint pen, magic ink and marker pen, especially can be used as ink-jet recording ink is applied in the image processing system such as printer in the ink-vapor recording, more particularly, this printer have during printing, before or after at 50 ℃ to 200 ℃ following heating papers or printing ink so that promote to print the fixed function.In addition, can be applied to suitably according to recording ink of the present invention according to print cartridge of the present invention, ink recorded matter, ink-jet recording device and ink jet recording method.

Print cartridge

Print cartridge of the present invention has recording ink of the present invention and other selectable unit (SU) as required in container.

To container without limits, can select suitably shape, structure, size and material according to purpose; Its preferred embodiment is by aluminium stacked film or the film formed China ink bag of resin.

To print cartridge be described with reference to Fig. 1 and 2.Fig. 1 is exemplary print cartridge of the present invention, and Fig. 2 represents to be contained in the print cartridge in shell or the outer packaging.

Printing ink is from the China ink bag 241 of ink inlet 242 introducing print cartridges 200, and China ink bag 241 degasification and ink inlet 242 seal by melting then, as shown in Figure 1.In use, by puncturing ink export 243, printing ink is fed in the device as rubber components.

China ink bag 241 is formed by bubble-tight wrapping material such as aluminium stacked film usually.As shown in Figure 2, China ink bag 241 is contained in the plasticity print cartridge shell 244 usually and is releasably attached to various ink-jet recording device.

Print cartridge of the present invention has recording ink of the present invention and uses by being releasably attached to various ink-jet recording device, and especially preferably is installed to after a while the ink-jet recording device of describing of the present invention and uses.

Ink-jet recording device and ink jet recording method

Ink-jet recording device of the present invention has ink jet unit and other optional unit at least as stimulating generation unit and control unit.

Ink jet recording method of the present invention contains the ink jet step at least and other optional step produces step and controlled step as stimulating.Ink jet recording method of the present invention can carry out suitably by ink-jet recording device of the present invention; The ink jet step can be carried out suitably by the ink jet unit.Ink jet step and ink jet unit

Thereby the ink jet step is to spray the step that recording ink of the present invention forms image by stimulation being applied to recording ink.

Thereby the ink jet unit is to spray the unit that recording ink of the present invention forms image by stimulation being applied to recording ink.Ink jet can be selected according to using suitably; The example comprises the various nozzles that are used for spray ink Printing.

Stimulation can be selected according to using suitably; The example comprises heat, pressure, vibration and light.These can be used alone or in combination of two or more.Wherein, heat and pressure are preferred.

Stimulate the example of generation unit to comprise heater element, pressurization device, piezoelectric element, vibration generator spare, ultrasonator and light, particularly, piezo-activator such as piezoelectric element, adopt electrothermal conversioning element such as heating resistive element to utilize the heat energy actuator of the phase transformation of liquid membrane boiling generation, utilize the shape memory alloy actuator of the metal phase change that thermal distortion produces and utilize the electrostatic actuator of electrostatic force.

The mode of injection record printing ink can be selected according to stimulating suitably; Producing by " heat " under the situation about stimulating, available such method wherein utilizes thermal head to pass through the pressure of bubble as nozzle bore injection and the discharge of drop from record-header to produce bubble and recording ink in recording ink by heat energy corresponding to the recording ink that the heat energy of recording signal is given in the record-header.Producing by " pressure " under the situation about stimulating, available such method, wherein crooked piezoelectric element also reduces volume in the pressure chamber by voltage being applied to the piezoelectric element that printing ink stream built-in in the record-header in the position that is called as the pressure chamber recording ink is sprayed as the nozzle bore of drop from record-header.

The drop size of the recording ink that sprays is preferably 3 to 40pl, and the speed of the drop that is sprayed is preferably 5 to 20m/s, and driving frequency is preferably more than the 1kHz, and resolving power is preferably more than the 300dpi.

Control unit can be selected suitably according to purpose; The example comprises the instrument as sequencer and computer.

Implement the embodiment of ink jet recording method of the present invention with ink-jet recording device of the present invention with reference to description of drawings.The paper that the ink-jet recording device that is shown in Fig. 3 has main body 101, be installed in paper feeding pallet 102 on the main body 101, be used to pile up the paper that has write down image on it is discharged pallet 103, print cartridge part 104.The function part 105 of operated key and indicating meter etc. is arranged on the print cartridge loading section 104.But print cartridge part 104 has the protecgulum 115 of opened/closed is used to remove print cartridge 201.

Shown in Figure 4 and 5, slide 133 keeps being free to slide on main scanning direction by tail rod 131 and stay 132, and by the mobile and scanning on the direction of arrow shown in Figure 5 of main scan motor (not shown), wherein this tail rod 131 is for laterally being bridged to the guiding parts of left side plate (not shown).

In slide 133, the record-header 134 that loading is made up of four statures of the ink droplets that sprays each color promptly yellow (Y), cyan (C), magenta (M) and black (B), make a plurality of ink jet openings arrange on the direction that intersects with main scanning direction, wherein the ink jet direction leads down.

The ink jet print head of record-header 134 can be following as the ink jet print head of energy production units with injection record printing ink for containing: piezo-activator such as piezoelectric element, adopt electrothermal conversioning element such as heating resistive element to utilize the heat energy actuator of the phase transformation that the film boiling of liquid produces, utilization utilizes the electrostatic actuator of electrostatic force by the shape memory alloy actuator of the metal phase change of thermal distortion generation.

Slide 133 has and is used to each color to supply the secondary groove 135 of each color ink.Recording ink of the present invention is fed to secondary groove 135 from the print cartridge of the present invention 201 that is installed in print cartridge loading section 105 by the supply pipe (not shown) that is used for recording ink.

Simultaneously, paper feeding is partly supplied the paper 142 that takes out on the paper sheet stacking part 141 of paper feeding pallet 102, it comprises first quarter moon forming roll or paper feeding roller 143 and separating pad 144 relative with paper feeding roller 143 and that be made up of the material with big frictional coefficient, this paper feeding roller 143 separates one by one and supplies with paper from paper sheet stacking part 141, and these separating pad 144 deflection paper feeding rollers 143 sides.

Be used for the supply that the paper that paper feeding is partly supplied supplies under the record-header 134A is partly had: supply with and be with 151, it is used for supplying with paper 142 by electrostatic attraction; Anti-roll 152, it supplies with paper 142 by being clipped in the middle from the paper 142 that the paper feeding part is sent into through guide rail 145 with 151 with supply; Supply with guide rail 153, it changes about 90 ° by the direction with paper and supplies with this paper of sending here near direction vertically upward on 151 in supply; And tip backer roll 156, it is supplied with by extruder member 154 deflections and is with 151 sides.Also comprise charging roller 156, it is for to the charging unit of supply with 151 surface-charged.

Supply is with 151 to be the endless belt, and it places between donor rollers 157 and the tensioning roller 158, and can move on the direction of the supply of band.This supply is with 151 to have: upper layer, its suction paper surface that following material forms of serving as reasons, the resin material that does not carry out resistance control that for example about 40 μ m are thick, for example multipolymer of tetrafluoroethylene and ethene; And backing layer (medium resistance layer, bottom), wherein to carrying out resistance control with carbon with this upper layer identical materials.Guiding parts 161 corresponding to the print area of record-header 134 is arranged at the dorsal part of supplying with 151.The paper discharge section that is used to discharge at the paper 142 of record-header 134 records comprises: be used for paper 142 is with 151 isolating separation nails 171, paper distributing roller 172 and is discharged first quarter moon forming roll 173 from supply.Paper is discharged pallet 103 and is arranged under the paper distributing roller 172.

Two-sided paper feeding unit 181 removably is carried on the posterior components of main body 101.This two-sided paper feeding unit 181 receives with the paper 142 that returns with the opposite direction of 151 sense of rotation with supply, this paper 142 is fed to anti-roll 152 once more oppositely and with it and supply is with between 151.Manual paper supply section 182 is arranged on the upper surface of two-sided paper feeding unit 181.

In this ink-jet recording device, paper 142 separates one by one and supply from paper feeding part, with near the paper 142 of vertically upward direction supply by guide rail 145 guiding, and by be clipped in supply be with 151 and anti-roll 152 between supply with.The paper tip further supply by being installed in pressure first quarter moon forming roll 155 places, top and changes about 90 ° of its direction of the supply with supply guide rail 153 guiding on 151.

Simultaneously, supply with and be with 157, and paper 142 is supplied with by electrostatic attraction by charging roller 156 chargings.Paper 142 places that slide 133 moved to stop according to picture signal come activation record head 134 with on the paper 142 that droplets of ink is ejected into stop with record delegation, and after supplying with paper 142 specified rates, write down next line.The signal that the end of recording operation by receiving record termination signal or paper 142 reaches posting field stops, and paper 142 is discharged to paper and discharges pallet 103 then.

When the residual content of recording ink is near the bottom in detecting secondary groove 135, the recording ink of specified rate is fed to secondary groove 135 from print cartridge 201.

In this ink-jet recording device, when the recording ink in the print cartridge 201 of the present invention was used up, the shell in the print cartridge 201 can be disassembled, and can only change the China ink bag of the inside.Even, also can stably supply recording ink when print cartridge constitutes with vertically arranged form when the front side loads.Therefore, even when being set to occupy the upside of main body 101, for example,, also can easily change print cartridge 201 even in being contained in support or object when having placed on the main body 101.

At this, the present invention is illustrated with tandem type (shuttle type), and wherein slide scans, and recording ink of the present invention can also be applied to have the line ink-jet recording device of line head similarly.

Ink-jet recording device of the present invention and ink jet recording method can be applied to the various records based on ink-jet recording system, for example, are applied to ink-vapor recording printer, picture unit, copy device, printer/facsimile recorder/duplicating machine compounding machine etc.

Ink recorded matter

Ink recorded matter of the present invention is that the mode by ink-jet recording device of the present invention and ink jet recording method of the present invention writes down.Ink recorded matter of the present invention has the image that forms with recording ink of the present invention on recording medium.

Recording medium can be selected suitably according to purpose; The example comprises common paper, glossy paper, dedicated paper, fabric, film, OHP sheet etc.These can be used alone or in combination.

Ink recorded matter of the present invention has high image quality, does not have ink bleed, and has excellent ageing stability, therefore, can be used to have printing, document or the file of various images and/or character suitably.

Embodiment

Refer now to embodiment and explain the present invention, but it should be understood that the present invention is not limited thereto at all.In the following description, except as otherwise noted, all parts and per-cent are in " quality ".

Preparation embodiment A-1

The solution A-1 of preparation polymeric dispersion stabilizer

Mixture of ingredients as follows is mixed with dissolving alpha-olefin/copolymer-maleic anhydride (I) with mechanical stirrer under heating, and the strainer with mean pore size 5 μ m filters micro-insoluble substance then, thus the solution A-1 of preparation polymeric dispersion stabilizer.

Alpha-olefin/copolymer-maleic anhydride (I) ^{* 1)}10.0 part

The 1N KOH aqueous solution ^{* 2)}68.62 part

21.38 parts of deionized waters

1) T-YP110, Seico PMC Co. system, the carbonatoms of alkene chain: 12 to 14, acid number: 385mgKOH/g, matter average molecular weight: 9000

2) alkali of 1.0 times of amounts is in acid number

Preparation embodiment A-2

The solution B of preparation polymeric dispersion stabilizer

Mixture of ingredients as follows is mixed with dissolving alpha-olefin/copolymer-maleic anhydride (II) with mechanical stirrer under heating, and the strainer with mean pore size 5 μ m filters micro-insoluble substance then, thus the solution B of preparation polymeric dispersion stabilizer.

Alpha-olefin/copolymer-maleic anhydride (II) ^{* 1)}10.0 part

The 1N NaOH aqueous solution ^{* 2)}28.08 part

61.92 parts of deionized waters

1) T-YP110, Seico PMC Co. system, the carbonatoms of alkene chain: 16 to 18, acid number: 221mgKOH/g, matter average molecular weight: 11000

2) alkali of 1.0 times of amounts is in acid number

Preparation embodiment A-3

The solution C of preparation polymeric dispersion stabilizer

Mixture of ingredients as follows is mixed with dissolving alpha-olefin/copolymer-maleic anhydride (III) with mechanical stirrer under heating, and the strainer with mean pore size 5 μ m filters micro-insoluble substance then, thus the solution C of preparation polymeric dispersion stabilizer.

Alpha-olefin/copolymer-maleic anhydride (III) ^{* 1)}10.0 part

The 1N LiOH aqueous solution ^{* 2)}17.34 part

72.66 parts of deionized waters

1) T-YP112, Seico PMC Co. system, the carbonatoms of alkene chain: 20 to 24, acid number 190mgKOH/g, matter average molecular weight: 10000

2) alkali of 1.2 times of amounts is in acid number

Preparation embodiment A-4

The solution D of preparation polymeric dispersion stabilizer

Mixture of ingredients as follows is mixed with dissolving alpha-olefin/copolymer-maleic anhydride (IV) with mechanical stirrer under heating, and the strainer with mean pore size 5 μ m filters micro-insoluble substance then, thus the solution D of preparation polymeric dispersion stabilizer.

Alpha-olefin/copolymer-maleic anhydride (IV) ^{* 1)}10.0 part

The 1N ammonia soln ^{* 2)}25.15 part

64.85 parts of deionized waters

1) T-YP113, Seico PMC Co. system, the carbonatoms of alkene chain: 16 to 18, acid number: 310mgKOH/g, matter average molecular weight: 11400

2) alkali of 1.5 times of amounts is in acid number

Embodiment A-1

Preparation pigment dispersion I

Monoazo yellow pigment ^{* 1)}20.0 part

Polyoxyethylene betanaphthyl ether (RT-100) ^{* 2)}6.6 part

73.4 parts of deionized waters

1) the C.I. Pigment Yellow 73 74, Dainichiseika Color ﹠amp; Chemicals Mfg.Co. system

2) nonionic surface active agent, the HLB value: 18.5, Takemoto Oil ﹠amp; Fat Co. system

At first, above-mentioned nonionic surface active agent is dissolved in deionized water with preparation solution, then this solution is mixed with abundant wetting above-mentioned pigment.KDLA Model Dyno-Mill wet type dispersion machine (WAB Machinery Co. system) with the zirconium oxide bead that is filled with the 0.5mm diameter disperses this mixture 4 hours under 2000rpm then, thus preparation primary pigment dispersion.Add the solution A-1 of above-mentioned polymeric dispersion stabilizer to this primary pigment dispersion with 20.0 parts amount, fully stir this mixture, thus preparation pigment dispersion I.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this pigment dispersion I ₅₀Be 49nm.

Embodiment A-2

Preparation pigment dispersion II

Quinacridone pigment (C.I. pigment red 122) ^{* 1)}20.0 part

Polyoxyethylene lauryl ether (DKS NL-450) ^{* 2)}6.6 part

73.4 parts of deionized waters

1) Dainichiseika Color ﹠amp; Chemicals Mfg.Co. system

2) nonionic surface active agent, the HLB value: 18.3, Dai-ichi Kogyo Seiyaku Co. system

At first, above-mentioned nonionic surface active agent is dissolved in deionized water with preparation solution, then this solution is mixed with abundant wetting above-mentioned pigment.KDLA Model Dyno-Mill wet type dispersion machine (WAB Machinery Co. system) with the zirconium oxide bead that is filled with the 0.5mm diameter disperses this mixture 2 hours under 2000rpm then, thus preparation primary pigment dispersion.Add the solution B of above-mentioned polymeric dispersion stabilizer to this primary pigment dispersion with 20.0 parts amount, fully stir this mixture, thus preparation pigment dispersion II.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this pigment dispersion II ₅₀Be 81nm.

Embodiment A-3

Preparation pigment dispersion III

Phthalocyanine pigment ^{* 1)}20.0 part

Polyoxyethylene vinylbenzene phenyl ether ^{* 2)}6.6 part

73.4 parts of deionized waters

1) C.I. pigment Blue 15: 3, Dainichiseika Color ﹠amp; Chemicals Mfg.Co. system

2) Noigen EA-197, nonionic surface active agent, the HLB value: 17.5, Dai-ichi KogyoSeiyaku Co. system

At first, above-mentioned nonionic surface active agent is dissolved in deionized water with preparation solution, then this solution is mixed with abundant wetting above-mentioned pigment.KDLA Model Dyno-Mill wet type dispersion machine (WAB Machinery Co. system) with the zirconium oxide bead that is filled with the 0.5mm diameter disperses this mixture 2 hours under 2000rpm then, thus preparation primary pigment dispersion.Add the solution C of above-mentioned polymeric dispersion stabilizer to this primary pigment dispersion with 20.0 parts amount, fully stir this mixture, thus preparation pigment dispersion III.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this pigment dispersion III ₅₀Be 83nm.

Embodiment A-4

Preparation pigment dispersion IV

Silicon-dioxide/dual-azo yellow composite pigment ^1*)24 parts

Dioctyl sodium sulphosuccinate (Newcol 291M) ^{* 2)}8 parts

68 parts of deionized waters

1) inorganic/organic ratio: 1/1, primary particle size: 17nm, Toda Kogyo Co. system

2) anion surfactant, Nippon Nyukazai Co. system

At first, above-mentioned tensio-active agent is dissolved in deionized water with preparation solution, then this solution is mixed with abundant wetting above-mentioned pigment.KDLAModel Dyno-Mill wet type dispersion machine (WAB Machinery Co. system) with the zirconium oxide bead that is filled with the 0.5mm diameter disperses this mixture 2 hours under 2000rpm then, thus preparation primary pigment dispersion.Add the solution C of above-mentioned polymeric dispersion stabilizer to this primary pigment dispersion with 20.0 parts amount, fully stir this mixture, thus preparation pigment dispersion IV.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this pigment dispersion IV ₅₀Be 39nm.

Embodiment A-5

Preparation pigment dispersion V

Silicon-dioxide/quinacridone PR122 composite pigment ^1*)28 parts

Anion surfactant High Tehnol NF-17 ^{* 2)}9.2 part

62.8 parts of deionized waters

1) inorganic/organic ratio: 1/1, primary particle size: 16nm, Toda Kogyo Co. system

2) polyoxyethylene vinylbenzene phenyl ether ammonium sulphonate, Dai-ichi Kogyo Seiyaku Co. system

At first, above-mentioned tensio-active agent is dissolved in deionized water with preparation solution, then this solution is mixed with abundant wetting above-mentioned pigment.KDLAModel Dyno-Mill wet type dispersion machine (WAB Machinery Co. system) with the zirconium oxide bead that is filled with the 0.5mm diameter disperses this mixture 2 hours under 2000rpm then, thus preparation primary pigment dispersion.Add the solution B of above-mentioned polymeric dispersion stabilizer to this primary pigment dispersion with 21.0 parts amount, fully stir this mixture, thus preparation pigment dispersion V.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this pigment dispersion V ₅₀Be 75nm.

Embodiment A-6

Preparation pigment dispersion VI

Silicon-dioxide/phthalocyanine PB15:3 composite pigment ^1*)24 parts

Polyoxyethylene lauryl ether (DKS NL-180) ^{* 2)}8 parts

68 parts of deionized waters

2) nonionic surface active agent, the HLB value: 16.2, Dai-ichi Kogyo Seiyaku Co. system

At first, above-mentioned tensio-active agent is dissolved in deionized water with preparation solution, then this solution is mixed with abundant wetting above-mentioned pigment.KDLAModel Dyno-Mill wet type dispersion machine (WAB Machinery Co. system) with the zirconium oxide bead that is filled with the 0.5mm diameter disperses this mixture 2 hours under 2000rpm then, thus preparation primary pigment dispersion.Add the solution C of above-mentioned polymeric dispersion stabilizer to this primary pigment dispersion with 20.0 parts amount, fully stir this mixture, thus preparation pigment dispersion VI.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this pigment dispersion VI ₅₀Be 78nm.

Embodiment A-7

Preparation pigment dispersion VII

Silicon-dioxide/dual-azo yellow composite pigment ^{* 1)}24 parts

Polyoxyethylene lauryl ether (DKS NL-450) ^{* 2)}8 parts

20 parts of the solution C of polymeric dispersion stabilizer

68 parts of deionized waters

At first, above-mentioned tensio-active agent is dissolved in deionized water with preparation solution, then this solution is mixed with the solution C of polymeric dispersion stabilizer with abundant wetting above-mentioned pigment.KDLA Model Dyno-Mill wet type dispersion machine (WAB Machinery Co. system) with the zirconium oxide bead that is filled with the 0.5mm diameter disperses this mixture 1.5 hours under 2000rpm then, thus preparation pigment dispersion VII.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this pigment dispersion VII ₅₀Be 39nm.

Embodiment A-8

Preparation pigment dispersion VIII

Silicon-dioxide/phthalocyanine PB15:3 composite pigment ^{* 1)}24 parts

Polyoxyethylene encircles phenyl ether more ^{* 2)}8 parts

68 parts of deionized waters

1) inorganic/organic ratio: 1/1 primary particle size: 16nm, Toda Kogyo Co. system

2) nonionic surface active agent, Newcol 780, the HLB value: 18.9, Nippon NyukazaiCo. system

At first, above-mentioned tensio-active agent is dissolved in deionized water with preparation solution, then this solution is mixed with abundant wetting above-mentioned pigment.KDLAModel Dyno-Mill wet type dispersion machine (WAB Machinery Co. system) with the zirconium oxide bead that is filled with the 0.5mm diameter disperses this mixture 2 hours under 2000rpm then, thus preparation primary pigment dispersion.Add the solution B of above-mentioned polymeric dispersion stabilizer to this primary pigment dispersion with 20.0 parts amount, fully stir this mixture, thus preparation pigment dispersion VIII.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this pigment dispersion VIII ₅₀Be 125nm.

Comparative examples A-1

Preparation pigment dispersion IX

Pigment dispersion IX prepares in the mode identical with the embodiment A-3 of preparation pigment dispersion III, except not adding the solution C of polymeric dispersion stabilizer.According to the measurement of adopting UPA-EX150 (MicroTrack Co. system), the median size D of this pigment dispersion IX ₅₀Be 81nm.

Comparative examples A-2

Preparation pigment dispersion X

Pigment dispersion X prepares in the mode identical with the embodiment A-3 of preparation pigment dispersion III, except the solution C of polymeric dispersion stabilizer becomes the solution E of showing vinylbenzene/maleic acid down.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this pigment dispersion X ₅₀Be 85nm.

The solution E of vinylbenzene/maleic acid: Polymaron 351S, acid number: 560mgKOH/g, molecular-weight average: 100000 to 110000, solid content: 10.2%, Arakawa Chemical Industries system

Embodiment A-9

The preparation recording ink

36 parts of pigment dispersion I

Boncoat 4001 (water-borne acrylic type emulsion) ^1*)6 parts

10 parts of glycerine

25 parts of triglycols

2,2,4-trimethylammonium-1,4 parts of 3-pentanediols

Polyfox PF-151N (activeconstituents: 50%) ^{* 2)}2 parts

Proxel LV (antiseptic-germicide/anti-mycotic agent) ^{* 3)}0.2 part

0.1 part of trolamine

16.7 parts of deionized waters

1) solid content: 50%, MFT:5 ℃, median size: 100nm, Dainippon Ink ﹠amp; Chemicals, the Inc. system

2) oligomeric non-ionic type fluorochemical surfactant, Omnova Co. system

3) 1, the 2-benzisothiazole-3-ketone, activeconstituents: 20%, have dipropylene glycol, the AveciaCo. system

With above-mentioned Boncoat 4001, glycerine, triglycol, 2,2,4-trimethylammonium-1,3-pentanediol, PolyfoxPF-151N, Proxel LV and trolamine are dissolved in deionized water with the preparation carrier, this carrier mixes with pigment dispersion I with the preparation mixture, is the recording ink of the rhodia film filter press filtration of 0.8 μ m with preparation embodiment A-9 then by mean pore size with this mixture.

Embodiment A-10

The preparation recording ink

42 parts of pigment dispersion II

Hydran HW-940 (solid content: 50%) ^{* 1)}7 parts

6 parts of glycerine

The 3-methyl isophthalic acid, 19 parts of 3-butyleneglycols

2-ethyl-1,2 parts of 3-hexylene glycols

Zoneal FS-300 (activeconstituents: 40%) ^{* 2)}2.5 part

Proxel LV (antiseptic-germicide/anti-mycotic agent) ^{* 3)}0.2 part

2-amino-2-ethyl-1,0.1 part of ammediol

18.2 parts of deionized waters

1) polyester/polyurethane water-based ionomer, MFT:0 ℃, median size: 20nm, DainipponInk ﹠amp; Chemicals, the Inc. system

2) polyoxyethylene perfluoroalkyl ethers, DuPont Co. system

With above-mentioned Hydran HW-940, glycerine, 3-methyl isophthalic acid, 3-butyleneglycol, 2-ethyl 1,3-hexylene glycol, Zoneal FS-300, Proxel LV and 2-amino-2-ethyl-1, ammediol is dissolved in deionized water with the preparation carrier, this carrier mixes with pigment dispersion II with the preparation mixture, is the recording ink of the rhodia film filter press filtration of 0.8 μ m with preparation embodiment A-10 then by mean pore size with this mixture.

Embodiment A-11

The preparation recording ink

36 parts of pigment dispersion III

Acrit WEM-321U (solid content: 38%) ^{* 1)}7.9 part

7.5 parts of glycerine

22.5 parts of 1,3 butylene glycols

2-ethyl-1,4.0 parts of 3-hexylene glycols

Polyfox PF-156A (activeconstituents: 30%) ^{* 2)}3.3 part

Proxel LV (antiseptic-germicide/anti-mycotic agent) ^{* 3)}0.2 part

2-amino-2-ethyl-1,0.1 part of ammediol

18.5 parts of deionized waters

1) acrylic acid or the like/polyurethane aqueous emulsion, MFT:10 ℃, median size: 100nm, TaiseiKako Co. system

2) anionic fluorosurfactants, Omnova Co. system

With above-mentioned Acrit WEM-321U, glycerine, 1,3-butyleneglycol, 2-ethyl-1,3-hexylene glycol, PolyfoxPF-156A, Proxel LV and 2-amino-2-ethyl-1, ammediol is dissolved in deionized water with the preparation carrier, this carrier mixes with pigment dispersion III with the preparation mixture, is the recording ink of the rhodia film filter press filtration of 0.8 μ m with preparation embodiment A-11 then by mean pore size with this mixture.

Embodiment A-12

The preparation recording ink

35 parts of pigment dispersion IV

Boncoat 4001 (water-borne acrylic type emulsion) ^1*)7.0 part

7.5 parts of glycerine

22.5 parts of glycol ethers

2,2,4-trimethylammonium-1,4.0 parts of 3-pentanediols

Polyfox PF-151N (activeconstituents: 50%) ^{* 2)}2.0 part

Proxel LV (antiseptic-germicide/anti-mycotic agent) ^{* 3)}0.2 part

2-amino-2-ethyl-1,0.1 part of ammediol

21.7 parts of deionized waters

2) oligomeric non-ionic type fluorochemical surfactant, Omnova Co. system

With above-mentioned Boncoat 4001, glycerine, glycol ether, 2,2,4-trimethylammonium-1,3-pentanediol, PolyfoxPF-151N, Proxel LV and 2-amino-2-ethyl-1, ammediol is dissolved in deionized water with the preparation carrier, this carrier mixes with pigment dispersion IV with the preparation mixture, is the recording ink of the rhodia film filter press filtration of 0.8 μ m with preparation embodiment A-12 then by mean pore size with this mixture.

Embodiment A-13

The preparation recording ink

38.9 parts of pigment dispersion V

Hydran HW-940 (solid content: 50%) ^{* 1)}9.0 part

6.0 parts of glycerine

The 3-methyl isophthalic acid, 19 parts of 3-butyleneglycols

2-ethyl-1,2.0 parts of 3-hexylene glycols

Zoneal FS-300 (activeconstituents: 40%) ^{* 2)}2.5 part

Proxel LV (antiseptic-germicide/anti-mycotic agent) ^{* 3)}0.2 part

0.1 part of trolamine

18.2 parts of deionized waters

2) polyoxyethylene perfluoroalkyl ethers, DuPont Co. system

With above-mentioned Hydran HW-940, glycerine, 3-methyl isophthalic acid, 3-butyleneglycol, 2-ethyl-1,3-hexylene glycol, Zoneal FS-300, Proxel LV and trolamine are dissolved in deionized water with the preparation carrier, this carrier mixes with pigment dispersion V with the preparation mixture, is the recording ink of the rhodia film filter press filtration of 0.8 μ m with preparation embodiment A-13 then by mean pore size with this mixture.

Embodiment A-14

The preparation recording ink

35 parts of pigment dispersion VI

Acrit WEM-321U (solid content: 38%) ^{* 1)}7 parts

7.5 parts of glycerine

22.5 parts of 1,3 butylene glycols

2-ethyl-1,4 parts of 3-hexylene glycols

Polyfox PF-156A (activeconstituents: 30%) ^{* 2)}3.3 part

Proxel LV (antiseptic-germicide/anti-mycotic agent) ^{* 3)}0.2 part

2-amino-2-ethyl-1,0.1 part of ammediol

20.4 parts of deionized waters

1) acrylic acid or the like/polyurethane aqueous emulsion, MFT:10 ℃, median size: 100nm, Taisei KakoCo. system

2) anionic fluorosurfactants, Omnova Co. system

With above-mentioned Acrit WEM-321U, glycerine, 1,3-butyleneglycol, 2-ethyl-1,3-hexylene glycol, PolyfoxPF-156A, Proxel LV and 2-amino-2-ethyl-1, ammediol is dissolved in deionized water with the preparation carrier, this carrier mixes with pigment dispersion VI with the preparation mixture, is the recording ink of the rhodia film filter press filtration of 0.8 μ m with preparation embodiment A-14 then by mean pore size with this mixture.

Embodiment A-15

The preparation recording ink

35 parts of pigment dispersion VII

Boncoat 4001 (water-borne acrylic type emulsion) ^1*)7 parts

7.5 parts of glycerine

The 3-methyl isophthalic acid, 22.5 parts of 3-butyleneglycols

2,2,4-trimethylammonium-1,4 parts of 3-pentanediols

Polyfox PF-151N (activeconstituents: 50%) ^{* 2)}2 parts

Proxel LV (antiseptic-germicide/anti-mycotic agent) ^{* 3)}0.2 part

2-amino-2-ethyl-1,0.1 part of ammediol

21.7 parts of deionized waters

2) oligomeric non-ionic type fluorochemical surfactant, Omnova Co. system

With above-mentioned Boncoat 4001, glycerine, 3-methyl isophthalic acid, 3-butyleneglycol, 2,2,4-trimethylammonium-1,3-pentanediol, Polyfox PF-151N, Proxel LV and 2-amino-2-ethyl-1, ammediol is dissolved in deionized water with the preparation carrier, and this carrier mixes with pigment dispersion VII with the preparation mixture, is the recording ink of the rhodia film filter press filtration of 0.8 μ m with preparation embodiment A-15 then by mean pore size with this mixture.

Embodiment A-16

The preparation recording ink

The recording ink of embodiment A-16 prepares in the mode identical with embodiment A-14, except pigment dispersion VI changes into pigment dispersion VIII.

Comparative examples A-3

The preparation recording ink

The recording ink of Comparative examples A-3 prepares in the mode identical with embodiment A-14, except using Softanol EP-5035 (polyoxyethylene polyoxypropylene branched-alkyl ether, activeconstituents: 100%, NipponShokubai Co. system) replaces Polyfox PF-156A, make the amount of two kinds of activeconstituentss equate, regulate addition and additional deionized water simultaneously.

Comparative examples A-4

The preparation recording ink

The recording ink of Comparative examples A-4 prepares in the mode identical with embodiment A-9, except not using Boncoat 4001.

Comparative examples A-5

The preparation recording ink

The recording ink of Comparative examples A-5 prepares in the mode identical with embodiment A-10, except not using Zoneal FS 300.

Comparative examples A-6

The preparation recording ink

The recording ink of Comparative examples A-6 prepares in the mode identical with embodiment A-11, changes into the pigment dispersion IX of comparative example 1 except pigment dispersion III.

Comparative examples A-7

The preparation recording ink

The recording ink of Comparative examples A-7 prepares in the mode identical with embodiment A-11, changes into the pigment dispersion X of comparative example 2 except pigment dispersion III.

Comparative examples A-8

The preparation recording ink

Printing ink is formed

C.I. Xylene Red 52 (water-soluble dye) is 3 parts

5 parts of glycerine

15 parts of glycol ethers

2-ethyl-1,2 parts of 3-hexylene glycols

Polyoxyethylene (n=18) lauryl ether ^{* 1)}1 part

0.2 part of Sodium dehydroacetate

8 parts of deionized waters

1) nonionic surface active agent, HLB:16.2, Dai-ichi Kogyo Seiyaku Co. system

The composition that stirs mentioned component is with preparation solution, with the lithium hydroxide aqueous solution of 10 quality % the pH value of this solution is adjusted to about 10 then, thereby preparing thick printing ink, is the printing ink that contains dyestuff of this thick printing ink of rhodia film filter press filtration of 0.8 μ m with preparation Comparative examples A-8 with mean pore size then.

Embodiment A-9 is performed as follows the assessment of ink performance to the recording ink of A-8 gained to A-16 and Comparative examples A-3; And use ink-jet printer (IPSIO G707, Ricoh Co. system) behind the print cartridge of filling with these recording inks as illustrated in fig. 1 and 2, to assess the jet performance and the image of these recording inks.The results are shown in table 1.

Assessment stability (velocity of variation)

The stability of recording ink is based on store a week back median size D down at 50 ℃ under drying conditions ₅₀Velocity of variation assess.This velocity of variation is by following Equation for Calculating; Measurement according to UPA-EX150 (MicroTrack Co. system) records median size D ₅₀

D after velocity of variation=storage ₅₀D before the/storage ₅₀* 100

Surface tension

The static surface tension of the surface tension of recording ink on 25 ℃ platinum plate, recording with tensiometer (CBVP-Z, Kyowa Interface ScienceCo. system).

Measure the pH value

The pH value is measured with ISFET pH meter KS701 (Shindengen Electric ManufacturingCo. system) down at 23 ℃.

The assessment jetting stability

The jetting stability of each printing ink was assessed with under the following conditions admissible stopping (dormant) or decubation (resting period): printing ink is filled in the print cartridge and at the fixed time prints, lid or do not clean during the printing; Measure then and do not occur that injection direction departs from or not cause stopping or decubation that the variation of mass flow can reach.The print cartridge of filling with printing ink is installed on the ink-jet printer (IPSIO G707, Ricoh Company system); And according to following criterion evaluation jetting stability.

Evaluation criteria

A:600 is more than second

B:60 is more than second and less than 600 seconds

C: less than 60 seconds

Assessment color saturation and color density

Each recording ink that is contained in the print cartridge is contained in ink-jet printer (IPSIOG707, Ricoh Co. system) in the same manner as described above, and prints once image (solid image) on the spot.Use common paper to print test.After printing the thing drying, measure brightness with reflection beam splitting densometer (X-Rite Co. system).Calculate gained color saturation and Standard Colors saturation ratio (Japan Color Version 2, yellow: 91.34, magenta: 74.55, cyan: ratio 62.82) and according to following criterion evaluation.According to the densitometric measurement of X-Rite, the printing ink that does not satisfy the following standard of each color density is defined as C.

The evaluation criteria of each color: yellow: more than 0.7, magenta: more than 0.9, cyan: more than 0.9

The paper that is used for printing test

Common paper: My Paper SA (NBS Ricoh Co. system), XEROX 4024 (Fuji Xerox OfficeSupply system), PB Paper (Canon Inc. system)

Evaluation criteria

More than the A:0.8

More than the B:0.7 and less than 0.8

C: less than 0.7

The assessment scratch resistance

Rub back and forth 5 times with calico with the load of 900g by clock meter CM-1 (Toyo Seiki Seisaku-sho, Ltd system) with each printing portion that is similar to the image sample that the method for saturation ratio in measuring produce on glossy paper.Each sample of visual observation and according to following criterion evaluation then.

The paper that is used for printing test

Glossy paper: PM photo prints paper (gloss) (Seiko Epson Co. system), professional photo papers PR-101 (Canon Inc. system)

Evaluation criteria

A: seldom do not have image to come off or image around fuzzy

B: few images comes off, and some is fuzzy around the image

C: significant image comes off and image blurs on every side

The assessment water tolerance

Water droplet is dropped in to be similar to the method for color saturation in measuring on each printing portion of the image sample that forms on the common paper, and visual observation is printed the state of thing and according to following criterion evaluation then.

Evaluation criteria

A: basic not variation

B: vestige appears on every side in the printing portion that drips water droplet

C: ink bleed appears on every side in the printing portion that drips water droplet

Photostabilization

Will be similar to image sample that the method for saturation ratio in measuring form with Atlas burn-in test instrument Ci35AW to be equivalent to the 0.35W/m of outdoor sunlight ²The irradiation 24 hours under 70 ℃ and 50%RH and under 89 ℃ blackboard (black panel) temperature of xenon radiation (340nm).According to the color deterioration/change that obtains behind the criterion evaluation pre-irradiation as follows.

Evaluation criteria

A: basic not variation

B: perceive variation, but can accept

C: significant color deterioration/change

Table 1

The result of table 1 shows that embodiment A-9 is compared to the recording ink of A-8 with Comparative examples A-3 to the recording ink that contains pigment dispersion of the present invention of A-16 and shows excellent storage stability, and demonstrated the sharpness that is similar to dye ink and provided by the record thing that this recording ink obtains and have excellent in water resistance and excellent sunproof higher reliability.

Preparation Embodiment B-1

The solution B-1 of preparation water-soluble polymers

Alpha-olefin/copolymer-maleic anhydride (I) ^{* 1)}10.0 part

The 1N LiOH aqueous solution ^{* 2)}17.34 part

72.66 parts of deionized waters

1) by above-mentioned formula (1) expression, T-YP112, Seico PMC Co. system, the carbonatoms of alkene chain: 20 to 24, acid number: 190mgKOH/g, matter average molecular weight: 10000

2) alkali of 1.2 times of amounts is in acid number

The mixture of mentioned component mixes alpha-olefin/copolymer-maleic anhydride (I) of representing with dissolving following formula (I) by mechanical stirrer under heating, be that the strainer of 5 μ m filters out a spot of insoluble substance with mean pore size then, thereby make the solution B-1 of water-soluble polymers.

Preparation Embodiment B-2

Prepare surface treated black pigment dispersion

Carbon black (CTAB specific surface area: 150m ²/ g, DBP absorption value: 100ml/100g) add in the 2.5N sodium sulfonate solution of 3000ml, thereby then this mixture is stirred to react 10 hours oxygenated blacks down 300rpm, 60 ℃ with the amount of 90g.Filtering reacting liquid is used in the sodium hydroxide solution and isolating carbon black, then it is carried out outside ultrafiltration.Wash the carbon black that obtains with water, drying, and be distributed in the pure water with solid content 30%.

Afterwards, 6.52 parts of water-soluble polymerss (are represented by following formula (1), T-YP115, Seico PMC Co. system, the carbonatoms of alkene chain: 16 to 18, acid number: 221mgKOH/g, matter average molecular weight: 11000, gegenion: ammonium ion, activeconstituents: aqueous solution B 23%) adds in 100 parts of above-mentioned carbon black dispersions with preparation black pigment dispersion.According to the measurement of using UPA-EX150 (Micro Track Co. system), the median size D of black pigment dispersion ₅₀Be 106nm.

Preparation Embodiment B-3

Preparation yellow ultramarine surfactant dispersion

Monoazo yellow pigment ^{* 1)}30.0 part

Polyoxyethylene vinylbenzene phenyl ether ^{* 2)}10.0 part

60.0 parts of deionized waters

2) Noigen EA-177, nonionic surface active agent, the HLB value: 15.7, Dai-ichi KogyoSeiyaku Co. system

At first, above-mentioned tensio-active agent is dissolved in deionized water with preparation solution, then this solution is mixed with abundant wetting above-mentioned pigment.KDLAModel Dyno-Mill wet type dispersion machine (WAB Machinery Co. system) with the zirconium oxide bead that is filled with the 0.5mm diameter disperses this mixture 4 hours under 2000rpm then, thus preparation primary pigment dispersion.

Then, with 2.13 parts of aqurous ployurethanes (Takelack W-5661 as water-soluble polymers, Mitsui Takeda Chemicals, Inc. make, activeconstituents: 35.2%) aqueous solution and 2.93 parts of water-soluble polymerss (are represented by following formula (1), T-YP114, Seico PMC Co. system, the carbonatoms of alkene chain: 12 to 14, acid number: 385mgKOH/g, molecular weight: 9000, gegenion: ammonium ion, activeconstituents: aqueous solution C 25.6%) adds this primary pigment dispersion to and fully stirs this mixture with preparation yellow ultramarine surfactant dispersion.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this surface of pigments promoting agent dispersion ₅₀Be 49nm.

Preparation Embodiment B-4

Preparation red pigment surfactant dispersion

Quinacridone pigment (C.I. pigment red 122) ^{* 1)}30.0 part

Polyoxyethylene betanaphthyl ether (RT-100) ^{* 2)}10.0 part

60.0 parts of deionized waters

1) Dainichiseika Color ﹠amp; Chemicals Mfg.Co. system

At first, above-mentioned tensio-active agent is dissolved in deionized water with preparation solution, then this solution is mixed with abundant wetting above-mentioned pigment.KDLAModel Dyno-Mill wet type dispersion machine (WAB Machinery Co. system) with the zirconium oxide bead that is filled with the 0.5mm diameter disperses this mixture 2 hours under 2000rpm then, thus preparation primary pigment dispersion.

Then, water-soluble phenylethene/acrylic copolymer (JC-05 with 3.57 parts, Seico PMC Co. system, activeconstituents: 21%) and 2.97 parts of water-soluble polymerss (represent by following formula (1), T-YP116, SeicoPMC Co. system, the carbonatoms of alkene chain: 16 to 18, acid number: 280 to 310mgKOH/g, matter average molecular weight: 11400, gegenion: ammonium ion, activeconstituents: aqueous solution D 25.3%) adds in this primary pigment dispersion and fully stirs this mixture with preparation red pigment surfactant dispersion.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this surface of pigments promoting agent dispersion ₅₀Be 81nm.

Preparation Embodiment B-5

Preparation green pigment surfactant dispersion A

Phthalocyanine pigment ^{* 1)}30.0 part

Polyoxyethylene lauryl ether (DKS NL-450) ^{* 2)}10.0 part

60.0 parts of deionized waters

Then, with 2.51 parts of water-soluble polyesters (Nichigo polyester W-0030 as water-soluble polymers, Nippon Synthetic Chemical Industry Co. system, activeconstituents: 29.9%) aqueous solution and 3.26 parts of water-soluble polymerss (are represented by following formula (1), T-YP115, Seico PMC Co. system, the carbonatoms of alkene chain: 16 to 18, acid number: 221mgKOH/g, matter average molecular weight: 11000, gegenion: ammonium ion, activeconstituents: aqueous solution B 23%) adds in this primary pigment dispersion and fully stirs this mixture with preparation red pigment surfactant dispersion.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this surface of pigments promoting agent dispersion ₅₀Be 75nm.

Preparation Embodiment B-6

Preparation green pigment surfactant dispersion B

Phthalocyanine pigment ^{* 1)}30.0 part

Polyoxyethylene vinylbenzene phenyl ether ^{* 2)}10.0 part

60.0 parts of deionized waters

Then, add to the aqueous solution B-1 of the water-soluble polymers of 15.0 parts preparation Embodiment B-1 in this primary pigment dispersion and fully stir this mixture with preparation green pigment surfactant dispersion B.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this surface of pigments promoting agent dispersion ₅₀Be 83nm.

Preparation Embodiment B-7

Preparation green pigment surfactant dispersion C

Phthalocyanine pigment ^{* 1)}30.0 part

Polyoxyethylene lauryl ether (DKS NL-450) ^{* 2)}10.0 part

60.0 parts of deionized waters

At first, above-mentioned tensio-active agent is dissolved in deionized water with preparation solution, then this solution is mixed with abundant wetting above-mentioned pigment.KDLAModel Dyno-Mill wet type dispersion machine (WAB Machinery Co. system) with the zirconium oxide bead that is filled with the 0.5mm diameter disperses this mixture 2 hours under 2000rpm then, thus preparation green pigment surfactant dispersion C.According to the measurement of adopting UPA-EX150 (Micro Track Co. system), the median size D of this surface of pigments promoting agent dispersion ₅₀Be 75nm.

Embodiment B-1 to B-11 and comparative example B-1 to B-6

The preparation recording ink

Printing ink prepares in the following manner.Wetting agent, penetrant, tensio-active agent and water are mixed to be shown in table 2,3 and 4 amount and composition, and stir 1 hour to form uniform mixture.In each mixture, add resin dispersion and stirred 1 hour, added pigment dispersion, antiseptic-germicide/anti-mycotic agent and defoamer and remix then 1 hour.The rhodia film filter press filtration that with each dispersion of gained by mean pore size is 0.8 μ m then is with removal coarse particles and impurity, thus the recording ink that preparation is used to assess.

Table 2

Table 3

Table 4

Table 2 to the composition in the table 4 is represented following material.

Acrylic acid or the like organic silicon emulsion: solid content: 40%, median size: 130nm, MFT:0 ℃ or lower, Toyo Ink Mfg.Co. system

Acrylic emulsions: John Clear 7600, solid content: 47%, median size: 90nm, MFT:10 ℃ or lower, Johnson Polymer Co. system

Polyaminoester emulsion: Hydran HW-930, solid content: 50%, median size: below the 200nm, MFT:0 ℃ or lower, DIC Co. system

Polyester emulsion: Pesresin A-520, solid content: 30%, median size: below the 100nm, MFT:30 ℃ or lower, Takamatsu Oil ﹠amp; Fat Co. system

Polyfox PF-151N: oligomeric non-ionic type fluorochemical surfactant, activeconstituents: 50%, Omnova Co. system

Zoneal FS-300: the polyoxyethylene perfluoroalkyl ethers, activeconstituents: 40%, DuPont Co. system

Softanol EP-5035: polyoxyethylene polyoxypropylene branched-alkyl ether, activeconstituents: 100%, Nippon Shokubai Co. system

Proxel GXL: main component: 1, the 2-benzisothiazole-3-ketone, anti-mycotic agent, activeconstituents: 20%, have dipropylene glycol, Avecia Co. system

KM-72F: the self-emulsifying silicone antifoam agent, activeconstituents: 100%, Shin-Etsu ChemicalCo. system

According to the recording ink of appraisal procedure as follows assessment Embodiment B-1 to B-11 and comparative example B-1 to B-6.The results are shown in table 5 and 6.

Amount of resin with respect to pigment

The ratio of the amount of resin dispersion and pigment solid content is by following calculating in the printing ink: ratio=resin solid content/pigment solid content.

The solid content of printing ink

The total solid content of pigment and resin (emulsion adding water soluble resin) in the acquisition printing ink.

Measure the viscosity of printing ink

The viscosity of printing ink is measured down at 25 ℃ with viscometer (RL-500, Toki Sangyo Co. system).

Measure the surface tension of printing ink

The surface tension of printing ink is measured down at 25 ℃ with automatic surface tonometer (CBVP-Z, Kyowa Interface ScienceCo. system).

Print the arrangement of assessment

Ink-jet printer (IPSIO G707, Ricoh Co. system) is set, thereby under the relative humidity of 23 ℃ temperature and 50%, the printing ink of equivalent is applied on the recording medium by the driving voltage of regulating on the piezoelectric element.

Jetting stability

To be printed on continuously on 200 the 6200 type paper (NBS Ricoh Co. system) with the chart that Microsoft Word 2000 (Microsoft Co.) image on the spot that form, every kind of color has been coated with A4 paper 5% area, assessment is sprayed and is disturbed then.According to the appended instruction manual of printer, from " common paper and standard are quick ", adjust, printing model is chosen as " not having color correction ".

Evaluation criteria

A: do not spray and disturb

B: some sprays interference

D: disturb significantly or not injection

Image density

To have 64 point symbols with what Microsoft Word 2000 (Microsoft Co.) formed

Chart be printed on Xerox 4024 paper (Fuji Xerox Co. system), measure symbol on the print surface with X-Rite 938

The color of part and according to the assessment of following evaluation criteria.According to the appended instruction manual of printer, from " common paper and standard are quick ", adjust, printing model is chosen as " not having color correction ".

Evaluation criteria

A: black 〉=1.3, yellow 〉=0.85, magenta 〉=0.95, cyan 〉=1.1

B:1.3＞black 〉=1.2,0.85＞yellow 〉=0.80,0.95＞magenta 〉=0.90,1.1＞cyan 〉=1.0

C:1.2＞black 〉=1.1,0.80＞yellow 〉=0.70,0.90＞magenta 〉=0.80,1.0＞cyan 〉=0.9

D:1.1＞black, 0.70＞yellow, 0.80＞magenta, 0.9＞cyan

Color emissivity

To form with Microsoft Word 2000 (Microsoft Co.) with above-mentioned image density in similarly chart be printed on Xerox 4024 paper (Fuji Xerox Co.) symbol of measuring on the print surface with X-Rite 938

Part.According to the appended instruction manual of printer, from " common paper and standard are quick ", adjust, printing model is chosen as " not having color correction ".Color saturation that calculating records and Standard Colors saturation ratio (Japan color ver.2, yellow: 91.34, magenta: 74.55, cyan: ratio 62.82) is to assess according to following evaluation criteria.

Evaluation criteria

More than the A:0.8

B: less than 0.8

Water tolerance

With with image density in similarly mode chart is printed on Xerox Type 6200 paper (NBSRicoh Co. system), then with the symbol on the print surface

Part under 23 ℃ temperature and 50%RH dry 24 hours.Then the exsiccant chart is immersed in 30 ℃ the water one minute, slowly take out, and appropriateness is dry, assesses by following evaluation criteria then.

Evaluation criteria

A: do not have the color ink bleed

B: some color ink bleed

Scratch resistance

The monochrome with 3cm * 3cm that will form with Microsoft Word 2000 (Microsoft Co.) chart of image on the spot is printed on the unglazed glossy paper that is exclusively used in Ricoh Gel Jet Printer (NBS Ricoh Co. system), the record thing that obtains under 23 ℃ and 50%RH dry 24 hours.Then, thereby will be by using double sticky tape attached to the 0803 cotton No.3 of the JIS L on the CM-1 type clock meter reciprocal 5 its printing portions that rub on the record thing, with the printing ink spot while subtracting background density on the X-Rite938 measurement cotton fabric, scratch resistance is assessed by following evaluation criteria then.

Evaluation criteria

A: spot density less than 0.1

The spot density that B:0.1 is above

Photostabilization

With with above-mentioned image density in similarly mode chart is printed on Type 6200 paper (NBSRicoh Co. system), then with the symbol on the print surface Part under 23 ℃ temperature and 50%RH dry 24 hours.This image section with Atlas burn-in test instrument Ci35AW to be equivalent to the 0.35W/m of outdoor sunlight ²The irradiation 24 hours under 70 ℃ and 50%RH and under 89 ℃ the blackboard temperature of xenon radiation (340nm).According to the color deterioration and the change that obtain behind the criterion evaluation pre-irradiation as follows.

Evaluation criteria

A: basic not variation

B: perceive variation, but can accept

C: significant color deterioration/change

Drying property

With with above-mentioned image density in similarly mode chart is printed on Type 6200 paper (NBSRicoh Co. system), then with the symbol on the print surface

Part is opened with filter immediately after printing and is contacted and push, the appearance of assessment transfer printing.

A: do not have transfer printing and spot

B: slight transfer printing and spot

C: remarkable transfer printing and spot

Table 5

Table 6

In comparative example B-2, too high viscosity has been disturbed normal printing.

In comparative example B-3, cross wetting agent in a small amount and hindered normal printing.

Mark "-" expression in the table 6 does not obtain data.

Industrial applicibility

According to printing ink of the present invention, comprise that according to pigment dispersion of the present invention, it must provide Excellent color emissivity, excellent picture quality and higher reliability, and not only at specific record paper On, and on common paper, can form the high-quality that has than high colour saturation and suitable tone Therefore image can be advantageously used in print cartridge, ink recorded matter, ink-jet recording apparatus and ink mist recording Method.

Can be applied to the ink mist recording process according to ink-jet recording apparatus of the present invention and ink jet recording method Various records, and especially be advantageously used in ink mist recording printer, facsimile machine, duplicator, And printer/facsimile machine/duplicator set composite.

Claims

1. pigment dispersion comprises pigment, pigment dispersing agent, polymeric dispersion stabilizer and water, and wherein this polymeric dispersion stabilizer is the alpha-olefin/copolymer-maleic anhydride of following formula (1) expression:

Formula (1)

In formula (1), R represents that alkyl and n are 30 to 100 integer.

2. according to the pigment dispersion of claim 1, the acid number of wherein said alpha-olefin/copolymer-maleic anhydride is 100 to 400mgKOH/g.

3. according to the pigment dispersion of claim 2, wherein said alpha-olefin/copolymer-maleic anhydride uses as the solution in basic solution or alkaline aqueous solution, and the alkali number in this basic solution or the alkaline aqueous solution is not less than the alkali number suitable with the acid number of described alpha-olefin/copolymer-maleic anhydride.

4. according to each pigment dispersion in the claim 1 to 3, wherein said pigment is pigment dyestuff or the composite pigment that has applied the mineral dye of pigment dyestuff.

5. according to the pigment dispersion of claim 4, wherein said pigment dyestuff is to be selected from a kind of in phthalocyanine pigment, quinacridone pigment and the monoazo yellow pigment.

6. according to one pigment dispersion in claim 4 and 5, wherein said inorganic pigment granules is to be selected from least a in titanium dioxide granule, silica dioxide granule, alumina particle, ferric oxide particles, iron hydroxide particle and the granules of stannic oxide.

7. according to each pigment dispersion in the claim 1 to 6, wherein said pigment dispersing agent is that anion surfactant and HLB value are a kind of in 10 to 20 the nonionic surface active agent.

8. according to each pigment dispersion in the claim 1 to 7, the median size D of wherein said pigment dispersion ₅₀Be not more than 150nm.

9. recording ink comprises according to each pigment dispersion, tensio-active agent, water-dispersed resin, wetting agent and water in the claim 1 to 8.

10. according to the recording ink of claim 9, wherein said tensio-active agent is a kind of in organic silicon surfactant and the fluorochemical surfactant.

11. according to one recording ink in claim 9 and 10, wherein said water-dispersed resin has the film forming ability after printing on the recording medium, and has and be not higher than 30 ℃ minimum film-forming temperature.

12. according to each recording ink in the claim 9 to 11, wherein said wetting agent is for being selected from glycerine, glycol ether, triglycol, 1,3 butylene glycol and 3-methyl isophthalic acid, at least a in the 3-butyleneglycol.

13. according to each recording ink in the claim 9 to 12, wherein said recording ink further comprises at least a pH regulator agent that is selected from hydramine, alkali metal hydroxide, ammonium hydroxide, phosphonium hydroxides and the alkaline carbonate, and the pH value of this recording ink is 7 to 11.

14. a recording ink comprises water dispersible tinting material, water-dispersed resin, wetting agent and water at least,

The content of this wetting agent is 20 to 35 quality % in this recording ink, and the ratio (A/B) that the solid content (B) of pigment satisfies them in the solid content of water-dispersed resin (A) and the water dispersible tinting material in the printing ink is 2 to 8 relation,

Formula (1)

In formula (1), R represents alkyl, and n is 30 to 100 integer.

15. a recording ink comprises water dispersible tinting material, water-dispersed resin, wetting agent and water at least,

This pigment has hydrophilic radical from the teeth outwards at least and is not having to show as water dispersible or water miscible from dispersed color under the situation of dispersion agent,

This polymeric dispersion stabilizer is the alpha-olefin/copolymer-maleic anhydride of following formula (1) expression, or at least a mixture in this alpha-olefin/copolymer-maleic anhydride and styrene/acrylic analog copolymer, water soluble polyurethane resin and the Polyester Resin Water Soluble,

Formula (1)

In formula (1), R represents alkyl, and n is 30 to 100 integer.

16. according to one recording ink in claim 14 and 15, wherein based on whole recording ink, the total content of described water dispersible tinting material and described water-dispersed resin is 12 to 40 quality %.

17. according to each recording ink in the claim 14 to 16, the matter average molecular weight of wherein said alpha-olefin/copolymer-maleic anhydride is not higher than 20000.

18. according to each recording ink in the claim 14 to 17, the acid number of wherein said alpha-olefin/copolymer-maleic anhydride is 100 to 400mgKOH/g, and it uses as the solution in basic solution or alkaline aqueous solution, and the alkali number that this basic solution or alkaline aqueous solution contain is not less than the alkali number suitable with the acid number of this alpha-olefin/copolymer-maleic anhydride.

19. according to each recording ink in claim 14 and 16 to 18, wherein said pigment dispersing agent is that anion surfactant and HLB value are a kind of in 10 to 20 the nonionic surface active agent.

20. according to the recording ink of claim 19, wherein said HLB value is that 10 to 20 nonionic surface active agent is a kind of in polyoxyethylene betanaphthyl ether, polyoxyethylene lauryl ether and the polyoxyethylene vinylbenzene phenyl ether.

21. according to each recording ink in the claim 14 to 20, wherein said water-dispersed resin is a kind of in vibrin, urethane resin, acrylic resin and the acrylic acid or the like silicone resin, and the minimum film-forming temperature of this water-dispersed resin is not higher than 30 ℃.

22. according to each recording ink in the claim 14 to 21, wherein said wetting agent is for being selected from glycerine, glycol ether, triglycol, 1,3 butylene glycol and 3-methyl isophthalic acid, at least a in the 3-butyleneglycol.

23. according to each recording ink in the claim 14 to 22, wherein said recording ink further comprises tensio-active agent, and this tensio-active agent comprises and is selected from least a in organic silicon surfactant and the fluorochemical surfactant.

24. according to each recording ink in the claim 9 to 23, the viscosity of wherein said recording ink is 5 to 20mPas under 25 ℃, and surface tension at 25 ℃ down for not being higher than 35mN/m.

25. a print cartridge comprises in container according to each recording ink in the claim 9 to 24.

26. an ink jet recording method comprises the ink jet step at least, wherein in this ink jet step, to applying stimulation according to each recording ink in the claim 9 to 24 with by it is sprayed document image.

27. according to the ink jet recording method of claim 26, wherein this stimulation is to be selected from least a in heat, pressure, vibration and the light.

28. an ink-jet recording device comprises the ink jet unit at least, wherein by this ink jet unit to applying stimulation according to each recording ink in the claim 9 to 24 with by it is sprayed document image.

29. according to the ink-jet recording device of claim 28, wherein this stimulation is to be selected from least a in heat, pressure, vibration and the light.

30. an ink recorded matter comprises the image that forms by according to each recording ink in the claim 9 to 24 on recording medium.