CN101525512A - Ink composition, ink composition for ink jet recording, ink jet recording method, method for producing ink jet recorded matter and ink jet recorded matter - Google Patents

Abstract

In order to provide an ink composition which is excellent in color development, stability and fixability and, more particularly, an ink for ink jet recording which is excellent in color development, stability and fixability, and is excellent as a textile ink for ink jet recording, an ink composition includes a dispersion element having an average particle diameter of 50 nm to 300 nm, which allows a pigment to be dispersed in water; and polymer fine particles synthesized using at least alkyl(meth)acrylate and/or cyclic alkyl(meth)acrylate, and a reactive compound having an ethylene unsaturated group and a reactive group as components thereof, having a glass transition temperature of -10 DEG C. or less, and having an acid value of 100 mgKOH/g or less.

Description

The manufacture method of ink composition, ink for inkjet recording liquid, ink jet recording method, ink jet printing thing and ink jet printing thing

Technical field

The present invention relates to the good ink composition of a kind of quality, stability and fixation performance.It is good and simultaneously as the manufacture method and the ink jet printing thing of the good ink for inkjet recording liquid of used for textiles ink for inkjet recording liquid, ink jet recording method, ink jet printing thing to relate in particular to quality, stability and fixation performance.

Background technology

When being recorded the paper lettering of body to conduct, the black liquid that in ink-vapor recording, uses need have do not spread and sink in ooze, drying property is good, can variously be recorded the even lettering in surface, adjacent color such as can not mix at characteristic in the lettering of polychromes such as colored lettering system.

In black liquid in the past, particularly use the black liquid of pigment, carried out mostly mainly suppressing of the infiltration of black liquid to the paper surface by suppressing perviousness, by staying the discussion that black drop guarantees the lettering quality, thereby be practical at the paper near surface.But, in the black liquid that suppresses the infiltration of paper,, particularly in the recycled writing paper of the composition that has mixed various paper, ooze owing to black liquid causes to spread and sink in to the difference of the imbibition characteristic of its various compositions owing to the difference of paper kind causes the difference of oozing of spreading and sinking in big.In addition, this China ink liquid exists that the drying behind the lettering needs the time, the problem of adjacent color generation colour mixture in the lettering of the polychrome system of colored lettering etc., in addition, in having used the black liquid of pigment, also exist because pigment remains in the surface of paper etc. and the problem of erasibility deterioration as the look material.

In order to solve this problem, the trial of having carried out making black liquid that the perviousness of paper is improved, this is in the interpolation of carrying out butylcarbitol (referring to Patent Document 1), as both research of interpolation (referring to Patent Document 3) of the interpolation (referring to Patent Document 2) of the Surfynol 465 (day letter chemistry system) of the tensio-active agent of alkyne diol system or butylcarbitol and Surfynol 465.In addition, carrying out in black liquid, using the research (with reference to patent documentation 4) of the ether of glycol ether.

In addition, under the situation of the black liquid that has used pigment, generally be difficult to when guaranteeing dispersing of pigments stability, improve the perviousness of black liquid, therefore and the range of choice of permeate agent is narrow, and the combination of glycol ethers and pigment also has in the past: use the example (referring to Patent Document 5) of triglycol monomethyl ether and make the example (referring to Patent Document 6) etc. of the ethers of spent glycol, glycol ether or triglycol in pigment.

In addition, as used for textiles, for example comprise (the referring to Patent Document 7) of having used dyestuff or relate to black liquid (referring to Patent Document 8) of tackiness agent etc.

No. 5156675 specification sheets of [patent documentation 1] United States Patent (USP)

No. 5183502 specification sheets of [patent documentation 2] United States Patent (USP)

No. 5196056 specification sheets of [patent documentation 3] United States Patent (USP)

No. 2083372 specification sheets of [patent documentation 4] United States Patent (USP)

[patent documentation 5] Japanese Patent spy opens clear 56-147861 communique

[patent documentation 6] Japanese patent laid-open 9-111165 communique

[patent documentation 7] Japanese kokai publication hei 2007-515561 communique

[patent documentation 8] Japanese kokai publication hei 2007-126635 communique

Yet the lettering quality of aqueous ink in the past can not be satisfied the demand, and particularly insufficient as used for textiles ink for inkjet recording liquid fixation performance, depth of shade, quality are also insufficient.In addition, pigment dispersion instability in the past in case exist tensio-active agent, glycol ethers etc. to have the material of hydrophilic portion and hydrophobic portion, then causes the desorption of dispersed polymeres from pigment easily, has the bad problem of black liquid storage stability.Common aqueous ink oozes spreading and sinking in of paper in order to reduce it, needs tensio-active agent, glycol ethers etc. to have materials such as hydrophilic portion and hydrophobic portion.Have following problem for the black liquid that does not use these materials: the perviousness to paper is insufficient, the kind of paper is restricted in order to carry out uniform lettering, causes the lettering decrease in image quality easily.

In addition, if that class additive (tensio-active agent, two (three) glycol monobutyl ethers, (two) propylene glycol monobutyl ether or 1 of alkyne diol system or alkynol system of in pigment dispersion in the past, using the present invention to use, 2-alkylene glycol or their mixture), then there is following problem: can not get secular storage stability, the solvability again of China ink liquid is bad, thereby the become end etc. of the nozzle that stops up easily ink gun of black liquid drying.

Summary of the invention

The present invention is for solving the invention of described problem, the ink composition that provides a kind of quality, stability and fixation performance good is provided its purpose, particularly provide a kind of quality, stability and fixation performance good and simultaneously as used for textiles China ink liquid ink for inkjet recording liquid good and black liquid from the ink for inkjet recording liquid of the ejection excellent in stability of ink gun.

The present invention is as described below.

(1) a kind of ink composition is characterized in that,

Described dispersion is for can being dispersion below the above 300nm of 50nm to the median size in the water with colo(u)rant dispersion, the second-order transition temperature of described high molecular particle for below-10 ℃, acid number is below the 100mgKOH/g, and use alkyl at least (methyl) acrylate and/or cyclic alkyl (methyl) acrylate and to have ethene be that the reactive compounds of unsaturated group and reactive group synthesizes as its constituent.

(2) according to described (1) described ink composition, it is characterized in that,

Described reactive base is a blocked isocyanate Huo oxazolinyl.

(3) according to described (1) or (2) described ink composition, it is characterized in that,

Described alkyl (methyl) acrylate and/or cyclic alkyl (methyl) acrylate are alkyl (methyl) acrylate of carbon number 1～24 and/or cyclic alkyl (methyl) acrylate of carbon number 3～24.

(4) according to each described ink composition in described (1)～(3), it is characterized in that,

Described dispersion for do not use dispersion agent just can be dispersed in the water median size as below the above 300nm of 50nm from disperse black carbon.

(5) according to each described ink composition in described (1)～(3), it is characterized in that,

Described dispersion be for can use polymkeric substance that the median size that pigment dyestuff is dispersed in the water is the dispersion below the above 300nm of 50nm, and the vinylbenzene conversion weight-average molecular weight that this polymkeric substance is surveyed by gel permeation chromatography (GPC) is more than 10000 below 200000.

(6) according to each described ink composition in described (1)～(5), it is characterized in that,

Described high molecular particle is more than 100000 below 1000000 by the measured vinylbenzene conversion weight-average molecular weight of gel permeation chromatography (GPC).

(7) according to each described ink composition in described (1)～(6), it is characterized in that, contain 1, the 2-alkylene glycol.

According to each described ink composition in described (1)～(7), it is characterized in that (8) containing alkyne diol is that tensio-active agent and/or alkynol are tensio-active agent.

(9) according to each described ink composition in described (1)～(8), it is characterized in that,

The content (quality %) of the more described pigment of the content of described high molecular particle (quality %) is many.

(10) a kind of ink for inkjet recording liquid is characterized in that, described ink for inkjet recording liquid is each described ink composition in described (1)～(9).

(11) a kind of ink jet recording method is characterized in that, has:

Described (10) described ink for inkjet recording liquid is printed onto operation on the cloth; And

This has been printed the operation of heat-treating below 200 ℃ more than 110 ℃ more than 1 minute that is distributed in of ink for inkjet recording liquid.

(12) preparation method of ink jet printing thing is characterized in that, has:

The described ink for inkjet recording liquid of claim 10 is printed onto operation on the cloth; And

This has been printed the operation of heat-treating below 200 ℃ more than 110 ℃ more than 1 minute that is distributed in of ink for inkjet recording liquid.

(13) a kind of ink jet printing thing is characterized in that, the manufacture method by described (11) described ink jet recording method or described (12) described ink jet printing thing obtains.

The present invention is good in view of quality, stability and fixation performance just, particularly as the requirement of good etc. the characteristic of used for textiles ink for inkjet recording liquid, carried out the result who concentrates on studies.

Embodiment

Ink composition of the present invention is characterised in that, contain dispersion and high molecular particle, wherein, described dispersion is for can being dispersion below the above 300nm of 50nm to the median size in the water with colo(u)rant dispersion, the second-order transition temperature of described high molecular particle for below-10 ℃, acid number is below the 100mgKOH/g, and use at least and have reactive compounds that ethene is unsaturated group and reactive base and alkyl (methyl) acrylate and/or cyclic alkyl (methyl) acrylate and synthesize as its constituent.

Utilize described formation, improve as used for textiles and on cloth, give as security seal (Japanese: the metal to-metal contact in the time of the seal right-falling stroke) and the friction stability of wet friction.

In addition, ink jet recording method of the present invention is characterised in that to have: will be printed onto the operation on the cloth by the ink for inkjet recording liquid that described ink composition forms; And this has been printed the operation of heat-treating below 200 ℃ more than 110 ℃ 1 minute that is distributed in of black liquid.If discontented 110 ℃, then do not improve the fixation performance that is printed onto the black liquid on the cloth.If surpass 200 ℃, then deteriorations such as cloth, pigment and polymkeric substance.More preferably more than 120 ℃ and less than 170 ℃.Heat-up time, if less than 1 minute, then the reaction of various reactive groups such as blocked isocyanate, oxazolinyl can not fully be carried out preferably more than 1 minute.More preferably more than 2 minutes.

In addition, the manufacture method of ink jet printing thing of the present invention is characterised in that to have: will be printed onto the operation on the cloth by the ink for inkjet recording liquid that described ink composition forms; And to this cloth that has printed black liquid in the operation of heat-treating 1 minute more than 110 ℃ below 200 ℃.If less than 110 ℃, then do not improve the fixation performance that is printed onto the black liquid on the cloth.If surpass 200 ℃, then deteriorations such as cloth, pigment and polymkeric substance.More preferably more than 120 ℃ and less than 170 ℃.Heat-up time is preferred more than 1 minute, if less than 1 minute, then the reaction of various reactive groups such as blocked isocyanate, oxazolinyl can not fully be carried out.More preferably more than 2 minutes.

Below, the composition of ink composition is described.

Median size by described pigment dispersion of light scattering determining and high molecular particle.If through light scattering method and the median size of pigment dispersion less than 50nm, then quality decline.In addition, if the median size of pigment dispersion surpasses 300nm, then fixation performance descends.70nm～230nm more preferably, 80nm～130nm more preferably again.On the other hand, the particle diameter of high molecular particle is preferably below the above 500nm of 50nm, more preferably below the above 300nm of 60nm.If the particle diameter of high molecular particle is less than 50nm, then fixation performance descends.If it is surpass 500nm, then unstable easily from the ejection of ink gun.

In addition, the second-order transition temperature of high molecular particle is preferably below-10 ℃, and particularly the fixation performance as the pigment of textiles increases, if surpass-10 ℃, then the fixation performance of pigment slowly descends.More preferably-15 ℃, more more preferably-20 ℃.In addition, the acid number of high molecular particle is preferably below the 100mgKOH/g, if acid number surpasses 100mgKOH/g, then descends as the washing stability of used for textiles when cloth is given as security seal.50mgKOH/g more preferably is more more preferably below the 30mgKOH/g.

In addition, the molecular weight of high molecular particle is preferably more than 100,000, more preferably more than 200,000, if the washing stability when giving as security seal less than 100,000 then as used for textiles on cloth descends.

As alkyl (methyl) acrylate and/or cyclic alkyl (methyl) acrylate that are the constituent of high molecular particle, preferred carbon number is that 1～24 alkyl (methyl) acrylate and/or carbon number are 3～24 cyclic alkyl (methyl) acrylate, as its example, preferred (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, 2-ethylhexyl (methyl) acrylate, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, tert-butylcyclohexyl (methyl) acrylate, lauryl (methyl) acrylate, isobornyl (methyl) acrylate, (methyl) acrylate cetyl ester, (methyl) stearyl acrylate alcohol ester, (methyl) vinylformic acid isooctadecanol ester, tetramethyl-piperidyl (methyl) acrylate, two cyclopentyl (methyl) acrylate, dicyclopentenyl (methyl) acrylate, dicyclopentenyl oxygen base (methyl) acrylate and (methyl) vinylformic acid docosyl ester etc.

In addition, the reactive group that reactive compounds had as the constituent of high molecular particle is meant: the group of the reactions such as functional group that the functional group (for example hydroxyl that Mierocrystalline cellulose contained) that is had by suitable processing such as thermal treatment and cloth, the functional group that high molecular particle had or dispersion (resin etc.) have.Reactive group contains at least more than 1 in reactive compounds and gets final product, and also can contain a plurality of.On the other hand, the ethene in the reactive compounds is that unsaturated group is used for and reaction as alkyl (methyl) acrylate and/or cyclic alkyl (methyl) acrylate of the constituent outside the high molecular particle.

In the reactive group except comprising the group that this reactive group can react separately, also comprise blocked isocyanate and so on for example separately for inertia but through the reactive group of sensitizations such as heating.Blocked isocyanate is the free isocyanate group and compound (end-capping reagent) reaction that contains the active hydrogen base with the terminal precursor of the isocyanate group of making, become the inert material at normal temperatures, if to its heating, thus the end-capping reagent material of character of regeneration isocyanate group that dissociates then.

In the ink composition of the present invention, in order to be used in the used for textiles ink-vapor recording purposes, reactive group is preferably blocked isocyanate Huo oxazolinyl.

In addition, be the example of unsaturated group as the ethene that reactive compounds had of the constituent of high molecular particle, can enumerate as vinyl, (methyl) acryl etc.

As having the example that ethene is the reactive compounds of unsaturated group and blocked isocyanate, sale have clear and the electrician makes Karenz MOI-BM, Karenz MOI-BP etc.

As having ethene is that unsaturated group is with the reactive compounds of oxazolinyl, can enumerate as, castor-oil plant Chun oxazoline (methyl) acrylate, 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-pseudoallyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 2-pseudoallyl-2-oxazoline etc.Wherein, preferred castor-oil plant Chun oxazoline (methyl) acrylate.

In addition, in the ink composition of the present invention, as described dispersion preferably contain do not use dispersion agent just can be in water the dispersive median size for below the above 300nm of 50nm from disperse black carbon.Should can improve the quality of print from disperse black carbon by using.Do not use dispersion agent just can in water, the dispersive method have pair sooty surface to carry out method of oxidations such as ozone, clorox etc.Described median size from the disperse black carbon dispersion is preferably 50nm～150nm.If less than 50nm then can not obtain quality, if surpass 150nm then fixation performance descends.Preferred particle diameter is 70nm～130nm.Be preferably 80nm～120nm again.

In addition, in the ink composition of the present invention, as dispersion, preferably contain and can use polymkeric substance that the median size that pigment dyestuff is dispersed in the water is the dispersion below the above 300nm of 50nm, the vinylbenzene conversion weight-average molecular weight that this polymkeric substance is recorded by gel permeation chromatography (GPC) is more than 10000 below 200000.Thus, particularly the fixation performance as the pigment of used for textiles China ink liquid increases, and the storage stability of pigment inks liquid also increases.In addition, except that dispersion agent,, also can add polymkeric substance, the tensio-active agent of water dispersible or water-soluble as dispersion stabilizer in order to make stably dispersing.In addition, described polymkeric substance preferably serve as reasons more than at least 70 quality % as its constituent (methyl) acrylate and (methyl) acrylic acid copolymerization and polymkeric substance.

In addition, for the high molecular particle that ink composition of the present invention contains, the vinylbenzene conversion weight-average molecular weight that records is more than 100000 below 1000000 by gel permeation chromatography (GPC).Vinylbenzene conversion weight-average molecular weight is more than 100000 below 1000000, particularly increases as the fixation performance of the pigment of used for textiles China ink liquid thus.

In addition, ink composition of the present invention preferably uses 1, the 2-alkylene glycol.By using 1,2-alkylene glycol and permeate minimizing, printing quality increases, as 1, the example of 2-alkylene glycol, preferred 1,2-hexylene glycol, 1,2-pentanediol, 4-methyl isophthalic acid, the carbon number of 2-pentanediol and so on be 5 or 61, the 2-alkylene glycol.Wherein, preferred carbon number be 61,2-hexylene glycol and 4-methyl isophthalic acid, 2-pentanediol.In addition, 1, the addition of 2-alkylene glycol is preferably 0.3 quality %～30 quality %, more preferably 0.5 quality %～10 quality %.

In addition, ink composition of the present invention also can contain glycol ethers.As glycol ethers, can use one or more that from butylcarbitol, triglycol monobutyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether, select.In addition, the addition of glycol ethers is preferably 0.1 quality %～20 quality %, more preferably 0.5 quality %～10 quality %.

In addition, ink composition of the present invention also can contain glycol ethers.Can use one or more that from butylcarbitol, triglycol monobutyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether, select as glycol ethers.In addition, the addition of glycol ethers is preferably 0.1 quality %～20 quality %, more preferably 0.5 quality %～10 quality %.

In addition, preferably to contain alkyne diol be that tensio-active agent and/or alkynol are tensio-active agent to ink composition of the present invention.By using alkyne diol is that tensio-active agent and/or alkynol are tensio-active agent, can further reduce infiltration, improves printing quality.In addition,, can improve the drying property of lettering, realize high speed printing by adding these.

As alkyne diol is that tensio-active agent and/or alkynol are tensio-active agent, preferably from 2,4,7,9-tetramethyl--5-decine-4,7-glycol and 2,4,7,9-tetramethyl--5-decine-4, the alkylene oxide affixture of 7-glycol, 2,4-dimethyl-5-decine-4, the alkylene oxide affixture, 2 of 7-glycol, 4-dimethyl-5-decine-4-alcohol and 2, more than one that the alkylene oxide affixture of 4-dimethyl-5-decine-4-alcohol is selected.These can be used as E series such as Olfine104 series, OlfineE1010, day chemical Surfynol 465 of letter or the Surfynol 61 etc. of Air Products (Britain) and obtain.

In addition, among the present invention, by using from by described 1,2-alkylene glycol, described alkyne diol are that tensio-active agent and/or alkynol are to select one or more in the group that constitutes of tensio-active agent, described glycol ethers, can further reduce to spread and sink in and ooze.

In addition, in the black liquid of the present invention, the content of described high molecular particle (quality %) is preferably more than the content (quality %) of described pigment.By in the high molecular particle of mass unit interpolation, especially improve fixation performance as the pigment of used for textiles China ink liquid more than pigment.In addition, as used for textiles, be printed onto on the cloth after, by adding water or having added the operation that the water of tensio-active agent cleans, clean the water soluble component in the black liquid, high molecular particle strengthens the fixation performance of cloth thus, and erasibility is further improved.

As the pigment that contains in the contained dispersion of ink composition of the present invention, use as black ink liquid, carbon black (C.I. Pigment black 7) classes such as preferred especially furnace treated black, dim, acetylene black, channel black also can be used metal species such as copper oxide, ferriferous oxide (C.I Pigment black 11), titanium oxide, the black pigment dyestuffs such as (C.I. Pigment blacks 1) of benzene nitrile.

In addition, use as color ink liquid, can use C.I. Pigment Yellow 73-1 (fast yellow-G), 3,12 (dual-azo yellow AAA), 13,14,17,24,34,35,37,42 (Zh 1s), 53,55,74,81,83 (dual-azo yellow-HR), 93,94,95,97,98,100,101,104,108,109,110,117,120,128,138,153,155,180,185, C.I. Pigment red 1,2,3,5,17,22 (bright strong day red), 23,31,38,48:2 (permanent red 2B (Ba)), 48:2 (permanent red 2B (Ca)), 48:3 (permanent red 2B (Sr)), 48:4 (permanent red 2B (Mn)), 49:1,52:2,53:1,57:1 (brilliant carmine 6B), 60:1,63:1,63:2,64:1,81 (rhodamine 6G color lakes), 83,88,101 (iron oxide reds), 104,105,106,108 (cadmium reds), 112,114,122 (the quinacridone magenta 〉, 123,146,149,166,168,170,172,177,178,179,185,190,193,202,206,209,219, C.I. pigment violet 19,23, C.I. pigment orange 36, C.I. pigment blue 1,2,15 (phthalocyanine blue R), 15:1,15:2,15:3 (phthalocyanine blue G), 15:4,15:6 (phthalocyanine blue E 〉, 16,17:1,56,60,63, C.I. Pigment green 1,4,7,8,10,17,18,36 grades and so on are as the various pigment of toner.

In addition, described pigment can use dispersion machine to disperse, and dispersion machine can use commercially available various dispersion machines.From polluting few angle, preferably use non-medium to disperse.As a specific example, can enumerate wet type fluid energy mill (jet mill) (Ji Nasi (ジ one Na ス) company), nanometer machine (nanometer fiber crops how company (Na モ Na one ザ company)), homogenizer (homogenizer) (Gu Lin (go-リ Application) company), Altimizer (the wild machinery of China fir) and Microfluidizer (Microfluidics company) etc.

The addition of the pigment when ink composition of the present invention is used as ink-vapor recording purposes China ink liquid is preferably 0.5 quality %～30 quality %, more preferably 1.0 quality %～15 quality %.The addition of less than 0.5 quality % can not be guaranteed lettering concentration, in addition, if for surpassing the addition of 30 quality %, the viscosity increase of black liquid then can occur or structural viscosity in viscosity characteristics, occur, thereby existence is from the trend of the ejection bad stability of the black liquid of ink gun.

In addition, in order to ensure the shelf-stability of ink composition of the present invention, from the stable ejection of ink gun, stop up or prevent that black liquid deterioration etc. from being purpose in order to improve, can add wetting Agent for Printing Inks, dissolution aids, infiltration inhibitor, viscosity modifier, pH and adjust agent, dissolution aids, antioxidant, sanitas, mould inhibitor, sanitas, be used to catch the various additives such as inner complex that influence the dispersive metal ion.

In addition, preferably by using piezoelectric element and so on not cause that the method for the electrostriction element of heating sprays ink composition of the present invention.Under the situation of the heating that causes hot shower nozzle (thermal head) and so on, used polymkeric substance takes place to go bad in the high molecular particle of interpolation, the dispersing of pigments etc., and is unstable thereby ejection becomes easily.Particularly when a large amount of black liquid are sprayed for a long time, preferably do not cause the head of heating.

Below, more specifically describe the present invention by embodiment.In addition, the present invention is not subjected to the qualification of these embodiment fully.In addition, during each of following each embodiment formed, " part ", " % " then referred to " mass parts ", " quality % " respectively unless otherwise specified.

Embodiment

(embodiment A-1)

(1) preparation of pigment dispersion A1

Pigment dispersion A1 uses the system MONARCH 880 of U.S. Cabot Co.,Ltd as carbon black (Pigment black 7).The same method of utilization and Japanese patent laid-open 8-3498 communique makes the sooty surface oxidation, and it is distributed in the water, becomes dispersion A1.Use Microtrac particle size distribution analyzer UPA250 (day machine dress system) to record particle diameter and be 110nm.

(2) preparation of high molecular particle

Ion exchanged water joined for 100 parts have dripping device, thermometer, the water-cooled reflux exchanger, in the reaction vessel of stirrer, while stirring in nitrogen atmosphere, add under 70 ℃ the condition as 0.2 part of the Potassium Persulphate of polymerization starter, be added with 0.05 part of Sodium Lauryl Sulphate BP/USP in 7 parts of ion exchanged waters, splashing under 70 ℃, 4 parts of glycidoxy acrylate, 15 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of tetrahydrofurfuryl acrylate, the monomer solution that 5 parts of butyl methacrylate and uncle's lauryl mercaptan are 0.02 part, make it reaction, make material 1 time.In this 1 material, add 2 parts of ammonium persulphate 10% solution, stir, add by 30 parts of ion exchanged waters while stirring down in 70 ℃ again, 0.2 part of lauryl potassium sulfate, 30 parts of ethyl propenoates, 25 parts of methyl acrylates, clear and electrician makes 6 parts of Karenz MOI-BM, 5 parts in vinylformic acid, the reaction solution of 0.5 part of formation of uncle's lauryl mercaptan, after making it to carry out polyreaction, neutralizing with sodium hydroxide, to transfer to pH be 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, with made high molecular particle aqueous dispersions as latex AA (EM-AA).After a part of taking out this high molecular particle aqueous dispersions made it drying, the vitrifying conversion temp of utilizing differential scanning calorimetry (Seiko-electronics system EXSTAR6000DSC) to record was-15 ℃.Using the gel permeation chromatography (GPC) of the system L7100 of Hitachi Co., Ltd series, is 150000 with THF as the vinylbenzene conversion molecular weight that solvent records.In addition, the acid number that is recorded by volumetry is 20mgKOH/g.

(3) preparation of ink for inkjet recording liquid

Below, the preferred group precedent in the ink for inkjet recording liquid is shown in Table 2.In the preparation of ink for inkjet recording liquid of the present invention, the dispersion A1 by use utilizes described method to be prepared from mixes and makes with the described vehicle of table 2 (vehicle) composition.In addition, the water of surplus uses and has added Mortopl Saden (ト Star プ サ イ De) 240 (the permachem asia corporate systems) 0.05%, the corrosive benzotriazole 0.02% that is used to prevent the ink gun parts that are used for preventing black corrosion respectively in ion exchanged water, be used to alleviate the water that EDTA (ethylenediamine tetraacetic acid (EDTA)) the 2Na salt 0.04% of the metal ion influence of black liquid system forms in related embodiment, reference example and the comparative example of embodiments of the present invention A.

(4) scuff test and the test of dry-cleaning property

Use the black liquid of embodiment A-1, ink-jet printer uses the system PX-V600 of Seiko Epson Corp, carries out full version printing on cotton, makes sample.Under 150 ℃, carried out heat treated 5 minutes.Use of Tai Site (テ ス -) the Industry Co., Ltd formula friction stability experimental machine AB-301S that shakes, under loading 300g to friction stability with this sample determination friction 200 times.According to the JIS L0849 of Japanese Industrial Standards (JIS) of the situation of peeling off of confirming black liquid, estimate with dry and moistening two standards.In addition, estimate the dry-cleaning test according to the B method of JIS L0860 equally.The table 1 that the results are shown in scuff test and dry-cleaning test.

The mensuration of (5) ejection stability

Ink-jet printer uses the system PX-V600 of Seiko Epson Corp, under 35 ℃, 35% atmosphere, XeroxP paper A4 in the zerox of Fuji corporate system opens, utilize standard, the MSP Gothic of character size size 11 among the Microsoft word, with the ratio of 4000 word/pages or leaves, print 100 pages and estimate.To not have the AA that is designated as of lettering confusion fully, the A that is designated as of 1 place's lettering confusion will be arranged, the B that is designated as of 2～3 place's lettering confusions will be arranged, the C that is designated as of 4～5 place's lettering confusions will be arranged, the D that is designated as of 6 place's lettering confusions will be arranged, show the result in table 1.

(embodiment A-2)

(1) preparation of pigment dispersion A2

At first, pigment dispersion A2 uses pigment Blue 15: 3 (CuPc pigment: Clariant system).With the reaction vessel that has stirrer, thermometer, return line and a dropping funnel with the nitrogen displacement after, add 75 parts of benzyl acrylates, 2 parts in vinylformic acid, 0.3 part of uncle's lauryl mercaptan, be heated to 70 ℃, in dropping funnel, add 1 part of other 20 parts of 1 part of 5 parts of 15 parts in 150 parts of benzyl acrylates, vinylformic acid, butyl acrylates, uncle's lauryl mercaptan, methyl ethyl ketones of preparing and Sodium Persulfate, in reaction vessel, drip the limit with 4 hours limits and make dispersed polymeres carry out polyreaction.Then, in reaction vessel, add methyl ethyl ketone, prepare the dispersing polymer solution of 40% concentration.Then, take out the part of this polymkeric substance, make it drying after, the second-order transition temperature that utilizes differential scanning calorimetry (Seiko Epson EXSTAR6000DSC) to record is 40 ℃.

In addition, with the pigment Blue 15 of 40 parts of described dispersing polymer solutions and 30 parts: 3 mix for 30 parts with 100 parts of aqueous sodium hydroxide solutions, the methyl ethyl ketone of 0.1mol/L.Use ultra-high voltage homogenizer (the wild machinery system of Co., Ltd. China fir Altimizer HJP-25005) then, under 200MPa, disperse by (pass) 15.Afterwards, be transferred to other containers and add 300 parts of ion exchanged waters, restir 1 hour.Afterwards, use rotary evaporator (rotary evaporator) that the water of whole methyl ethyl ketones and a part is boiled off, with the sodium hydroxide neutralization of 0.1mol/L, being adjusted to pH is 9.Filter with the filtering membrane of 0.3 μ m then, adjust, obtain pigment concentration and be 15% pigment dispersion A2 with ion exchanged water.The particle diameter that records with the method identical with embodiment A-1 is 80nm.

(2) preparation of high molecular particle

Ion exchanged water is joined for 100 parts in the reaction vessel that has dripping device, thermometer, water-cooled reflux exchanger, stirrer, under nitrogen, 70 ℃ condition, add as 0.2 part of the Potassium Persulphate of polymerization starter while stirring, in 7 parts of ion exchanged waters, splashing into the monomer solution that is added with 0.02 part of 0.05 part of Sodium Lauryl Sulphate BP/USP, 19 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of tetrahydrofurfuryl acrylate, 5 parts of butyl methacrylate and uncle's lauryl mercaptan under 70 ℃, make it reaction, make material 1 time.In this 1 material, adding ammonium persulphate 10% solution stirs for 2 parts, add by 30 parts of ion exchanged waters while stirring down in 70 ℃ again, 0.2 part of lauryl potassium sulfate, 30 parts of ethyl propenoates, 25 parts of methyl acrylates, 10 parts of butyl acrylates, clear and electrician makes 6 parts of KarenzMOI-BM, 5 parts in vinylformic acid, the reaction solution of 0.5 part of formation of uncle's lauryl mercaptan, after making it polyreaction, neutralizing with sodium hydroxide, to transfer to pH be 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, with made high molecular particle aqueous dispersions as latex AB (EM-AB).After a part of taking out this high molecular particle aqueous dispersions made it drying, the vitrifying conversion temp of utilizing differential scanning calorimetry (Seiko-electronics system EXSTAR6000DSC) to record was-17 ℃.By the vinylbenzene conversion molecular weight measured with the same method of embodiment A-1 is 200000.In addition, the acid number that is recorded by volumetry is 20mgKOH/g.

(3) preparation of ink for inkjet recording liquid

Below, the preferred group in the ink for inkjet recording liquid is become to be illustrated in table 2.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the described vehicle composition of table 2 and similarly make with embodiment A-1 by the dispersion A2 that use utilizes described method to be prepared from.

(4) scuff test and the test of dry-cleaning property

Use the black liquid of embodiment A-2, by carrying out scuff test and the test of dry-cleaning property with same method of embodiment A-1 and same evaluation method.The table 1 that the results are shown in scuff test and the test of dry-cleaning property.

The mensuration of (5) ejection stability

Use the black liquid of embodiment A-2, by spraying the mensuration of stability with same method of embodiment A-1 and same evaluation method.The measurement result of ejection stability is shown in table 1.

(embodiment A-3)

(1) preparation of pigment dispersion A3

At first, pigment dispersion A3 uses pigment violet 19 (quinacridone pigment: Clariant system) and similarly prepares with pigment dispersion A2, as pigment dispersion A3.By the particle diameter that records with the same method of embodiment A-1 is 90nm.

(2) preparation of high molecular particle

Use the high molecular particle identical with embodiment A-2.

(3) preparation of ink for inkjet recording liquid

Below, the preferred group of ink for inkjet recording liquid is become to be illustrated in table 2.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the vehicle shown in the table 2 and similarly be prepared and estimate with embodiment A-1 by the dispersion A3 that use utilizes described method to make.

(4) scuff test and the test of dry-cleaning property

Use the black liquid of embodiment A-3, by carrying out scuff test and the test of dry-cleaning property with same method of embodiment A-1 and same evaluation method.The table 1 that the results are shown in scuff test and the test of dry-cleaning property.

The mensuration of (5) ejection stability

Use the black liquid of embodiment A-3, by spraying the mensuration of stability with same method of embodiment A-1 and same evaluation method.The measurement result of ejection stability is shown in table 1.

(embodiment A-4)

(1) preparation of pigment dispersion A4

At first, pigment dispersion A4 uses pigment Yellow 14 (azo pigment: Clariant system) and similarly prepares with pigment dispersion A2, as pigment dispersion A4.By the particle diameter that records with the same method of embodiment A-1 is 115nm.

(2) preparation of high molecular particle

Use and the same high molecular particle of embodiment A-2.

(3) preparation of ink for inkjet recording liquid

Below, the preferred group of ink for inkjet recording liquid is become to be illustrated in table 2.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the vehicle shown in the table 2 and similarly be prepared and estimate with embodiment A-1 by the dispersion A4 that use utilizes described method to make.

(4) scuff test and the test of dry-cleaning property

Use the black liquid of embodiment A-4, by carrying out scuff test and the test of dry-cleaning property with same method of embodiment A-1 and same evaluation method.The table 1 that the results are shown in scuff test and the test of dry-cleaning property.

The mensuration of (5) ejection stability

Use the black liquid of embodiment A-4, by spraying the mensuration of stability with same method of embodiment A-1 and same evaluation method.The measurement result of ejection stability is shown in table 1

(Comparative examples A-1)

In the Comparative examples A-1, except the total amount (45 parts) with the ethyl propenoate in the embodiment A-1 changes to 45 parts of benzyl methacrylates, similarly carry out with embodiment A-1, except using second-order transition temperature is 0 ℃ the high molecular particle, similarly prepares black liquid with embodiment A-1 and estimates.The latex that uses this high molecular particle and make is called latex AC (EM-AC).Black liquid composition is shown in table 2.Scuff test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.Show the result in table 1.

(Comparative examples A-2)

In the Comparative examples A-2, except the total amount (49 parts) with the ethyl propenoate in the embodiment A-2 changes to benzyl methacrylate, 10 parts of butyl acrylates is changed to 10 parts of the benzyl methacrylates, similarly carry out with embodiment A-2, except using second-order transition temperature is 10 ℃ the high molecular particle, similarly prepares black liquid with embodiment A-2 and estimates.The latex that uses this high molecular particle and make is called latex AD (EM-AD).Black liquid composition is shown in table 2.Scuff test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.Show the result in table 1.

(Comparative examples A-3)

In the Comparative examples A-3,, similarly prepare black liquid with embodiment A-3 and estimate except the particle diameter of preparation pigment is the dispersion of 350nm and 45nm.By the method mensuration particle diameter same with embodiment A-1.With particle diameter is that the dispersion of 350nm is called pigment dispersion A3A, is that the dispersion of 45nm is called pigment dispersion A3B with particle diameter.Black liquid composition is shown in table 2.Scuff test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.Show the result in table 1.

(Comparative examples A-4)

In the Comparative examples A-4,, similarly prepare black liquid with embodiment A-4 and estimate except the acid number of the high molecular particle that will be in the embodiment A-4 adds become 120mgKOH/g and the 150mgKOH/g.The latex that the high molecular particle that uses acid number as 120mgKOH/g is prepared is called latex AE (EM-AE), and the latex that the high molecular particle that uses acid number as 150mgKOH/g is prepared is called latex AF (EM-AF).Black liquid composition is shown in table 2.Scuff test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.Show the result in table 1.

(Comparative examples A-5)

In the Comparative examples A-5, in not using embodiment A-2, have the blocked isocyanate (clear make KarenzM O I-B M with electrician) of (methyl) acryl, similarly prepare black liquid with embodiment A-2 and estimate.To use need not this have (methyl) acryl blocked isocyanate (clear and electrician makes KarenzM O I-B M) high molecular particle and the latex that makes is called latex AG (EM-AG), black liquid is formed be shown in table 2.Scuff test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.Show the result in table 1.

(Comparative examples A-6)

In the Comparative examples A-6, in not using embodiment A-3, have the blocked isocyanate (clear make Karenz M O I-B M with electrician) of (methyl) acryl, similarly prepare black liquid with embodiment A-3 and estimate.Black liquid composition is shown in table 2.Scuff test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.Show the result in table 1.

The result of the erasibility in table 1 embodiment A-1～4, the Comparative examples A-1～6, dry-cleaning property, ejection stability

The unit of Tg is ℃, and particle diameter is that the unit of nm, acid number is mgKOH/g in the median size unit of pigment.

Erasibility, dry-cleaning property are according to the metewand of JIS.

The black liquid of table 2 embodiment A-1～4 and Comparative examples A-1～6 is formed (quality %)

Pigment and polymer concentration divide expression with solid formation.

1,2-HD 1, the 2-hexylene glycol

1,2-PD 1, the 2-pentanediol

TEGmBE triglycol monobutyl ether

S-104 Surfynol 104 (a day letter chemistry system alkyne diol is a tensio-active agent)

S-465 Surfynol 465 (a day letter chemistry system alkyne diol is a tensio-active agent)

S-61 Surfynol 61 (a day letter chemistry system alkyne diol is a tensio-active agent)

The TMP TriMethylolPropane(TMP)

The TEG triglycol

The 2-P 2-Pyrrolidone

The TEA trolamine

(embodiment A-5)

(1) preparation of pigment dispersion A5

Pigment dispersion A5 uses the system MA100 of Mitsubishi Chemical Industrial Co., Ltd as carbon black (PBk7).The same method of utilization and Japanese patent laid-open 8-3498 communique makes the sooty surface oxidation and can be dispersed in the water, as dispersion A5.By the particle diameter that records with the same method of embodiment A-1 is 120nm.

(2) preparation of high molecular particle

Ion exchanged water is joined for 100 parts in the reaction vessel that has dripping device, thermometer, water-cooled reflux exchanger, stirrer, while stirring under nitrogen atmosphere, 70 ℃ condition, interpolation is as 0.3 part of the Potassium Persulphate of polymerization starter, make it reaction in 7 parts of ion exchanged waters, splashing into the monomer solution that is added with 0.02 part of 0.05 part of Sodium Lauryl Sulphate BP/USP, 20 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of lauryl acrylate, 5 parts of butyl methacrylate and uncle's lauryl mercaptan under 70 ℃, make material 1 time.In this 1 material, adding ammonium persulphate 10% solution stirs for 2 parts, add by 30 parts of ion exchanged waters while stirring down in 70 ℃ again, 0.2 part of lauryl potassium sulfate, 24 parts of ethyl propenoates, clear and electrician makes 6 parts of KarenzMOI-BM, 25 parts of butyl acrylates, 16 parts of lauryl acrylate, 5 parts in vinylformic acid, the reaction solution of 0.5 part of formation of uncle's lauryl mercaptan, after making it polyreaction, neutralizing with sodium hydroxide, to transfer to pH be 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, with made high molecular particle aqueous dispersions as being latex AI (EM-AI).After a part of taking out this high molecular particle aqueous dispersions made it drying, the vitrifying conversion temp of utilizing differential scanning calorimetry (Seiko-electronics system EXSTAR6000DSC) to record was-19 ℃.By the molecular weight measured with the same method of embodiment A-1 is 180000.In addition, the acid number that is recorded by volumetry is 18mgKOH/g.

(3) preparation of ink for inkjet recording liquid

Below, the preferred composition in the ink for inkjet recording liquid is illustrated in table 4.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the described vehicle composition of table 4 and similarly be prepared and estimate with embodiment A-1 by the dispersion A5 that use utilizes described method to be prepared from.

(4) scuff test and the test of dry-cleaning property

Use the black liquid of embodiment A-5, by carrying out scuff test and the test of dry-cleaning property with same method of embodiment A-1 and same evaluation method.The table 3 that the results are shown in scuff test and the test of dry-cleaning property.

The mensuration of (5) ejection stability

Use the black liquid of embodiment A-5, by spraying the mensuration of stability with same method of embodiment A-1 and same evaluation method.The measurement result of ejection stability is shown in table 3.

(embodiment A-6)

(1) preparation of pigment dispersion A6

At first, pigment dispersion A6 uses pigment Blue 15: 3 (CuPc pigment: Clariant system).With the reaction vessel that has stirrer, thermometer, return line and a dropping funnel with the nitrogen displacement after, add 45 parts of vinylbenzene, 30 parts in poly(oxyethylene glycol) 400 vinylformic acid, 10 parts of benzyl acrylates, 2 parts in vinylformic acid, 0.3 part of uncle's lauryl mercaptan, be heated to 70 ℃, in dropping funnel, add 5 parts of 1 part of 5 parts of 15 parts in 100 parts of 150 parts of vinylbenzene, poly(oxyethylene glycol) 400 acrylate, vinylformic acid, butyl acrylates, uncle's lauryl mercaptan preparing in addition and Sodium Persulfates, make the dispersed polymeres polymerization reaction take place with the limit of in reaction vessel, dripping, 4 hours limits.Then, in reaction vessel, add entry, prepare the dispersing polymer solution of 40% concentration.After a part of taking out this polymkeric substance made it drying, the second-order transition temperature that utilizes differential scanning calorimetry (Seiko Epson EXSTAR6000DSC) to record was 40 ℃.

In addition, with 40 parts of described dispersing polymer solutions and 30 parts of pigment Blue 15s: 3 mix for 100 parts with the aqueous sodium hydroxide solution of 0.1mol/L, utilize the Iger grinding machine that has used zirconium oxide bead to disperse 2 hours.Afterwards, be transferred to other containers and add 300 parts of ion exchanged waters, restir 1 hour.Afterwards, use the sodium hydroxide neutralization of 0.1mol/L, being adjusted to pH is 9.Filter with the filtering membrane of 0.3 μ m afterwards, make solid formation branch (dispersed polymeres and pigment Blue 15: 3) be 20% dispersion A6.The particle diameter that records with the method identical with embodiment A-1 is 100nm.The molecular weight that records by the method identical with embodiment A-1 is 210000.

(2) preparation of high molecular particle

Ion exchanged water is joined for 100 parts in the reaction vessel that has dripping device, thermometer, water-cooled reflux exchanger, stirrer, under nitrogen atmosphere, 70 ℃ condition, add as 0.3 part of the Potassium Persulphate of polymerization starter while stirring, make it reaction in 7 parts of ion exchanged waters, splashing into the monomer solution that is added with 0.02 part of 0.05 part of Sodium Lauryl Sulphate BP/USP, 20 parts of ethyl propenoates, 25 parts of butyl acrylates, 6 parts of lauryl acrylate, 5 parts of butyl methacrylate and uncle's lauryl mercaptan under 70 ℃, make material 1 time.In this 1 material, adding ammonium persulphate 10% solution stirs for 2 parts, add by 30 parts of ion exchanged waters while stirring down in 70 ℃ again, 0.2 part of lauryl potassium sulfate, 14 parts of ethyl propenoates, clear and electrician makes 6 parts of KarenzMOI-BM, 20 parts of butyl acrylates, 20 parts of lauryl acrylate, 5 parts in vinylformic acid, the reaction solution of 0.5 part of formation of uncle's lauryl mercaptan, after making it polyreaction, neutralizing with sodium hydroxide, to transfer to pH be 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, with made high molecular particle aqueous dispersions as latex AJ (EM-AJ).After a part of taking out this high molecular particle aqueous dispersions made it drying, the vitrifying conversion temp of utilizing differential scanning calorimetry (Seiko-electronics system EXSTAR6000DSC) to record was-21 ℃.In addition, the acid number that is recorded by volumetry is 18mgKOH/g.

(3) preparation of ink for inkjet recording liquid

Below, the preferred composition in the ink for inkjet recording liquid is illustrated in table 4.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the described vehicle composition of table 4 and similarly be prepared and estimate with embodiment A-1 by the dispersion A6 that use utilizes described method to be prepared from.

(4) scuff test and the test of dry-cleaning property

Use the black liquid of embodiment A-6, by carrying out scuff test and the test of dry-cleaning property with same method of embodiment A-1 and same evaluation method.The table 3 that the results are shown in scuff test and the test of dry-cleaning property.

The mensuration of (5) ejection stability

Use the black liquid of embodiment A-6, by spraying the mensuration of stability with same method of embodiment A-1 and same evaluation method.The measurement result of ejection stability is shown in table 3.

(embodiment A-7)

(1) preparation of pigment dispersion A7

At first, pigment dispersion A7 uses pigment red 122 (dimethylquinacridone pigment: Clariant system), and similarly prepare with pigment dispersion A6.The particle diameter that the same method of utilization and embodiment A-1 records is 80nm.

(2) preparation of high molecular particle

Use and the same high molecular particle of embodiment A-6.

(3) preparation of ink for inkjet recording liquid

Below, the preferred group in the ink for inkjet recording liquid is become to be illustrated in table 4.In the preparation of ink for inkjet recording liquid of the present invention, use the dispersion A7 utilize described method to be prepared from, mix with the described vehicle composition of table 4 and similarly be prepared and estimate with embodiment A-1.

(4) scuff test and the test of dry-cleaning property

Use the black liquid of embodiment A-7, by carrying out scuff test and the test of dry-cleaning property with same method of embodiment A-1 and same evaluation method.The table 3 that the results are shown in scuff test and the test of dry-cleaning property.

The mensuration of (5) ejection stability

Use the black liquid of embodiment A-7, by spraying the mensuration of stability with same method of embodiment A-1 and same evaluation method.The measurement result of ejection stability is shown in table 3.

(embodiment A-8)

(1) preparation of pigment dispersion A8

At first, pigment dispersion A8 uses Pigment Yellow 73 180 (benzimidazolone is a disazo pigment: Clariant system), and similarly prepare with pigment dispersion A6.The particle diameter that the same method of utilization and embodiment A-1 records is 130nm.

(2) preparation of high molecular particle

Use and the same high molecular particle of embodiment A-6.

(3) preparation of ink for inkjet recording liquid

Below, the preferred group in the ink for inkjet recording liquid is become to be illustrated in table 4.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the described vehicle composition of table 4 and similarly be prepared and estimate with embodiment A-1 by the dispersion A8 that use utilizes described method to be prepared from.

(4) scuff test and the test of dry-cleaning property

Use the black liquid of embodiment A-8, by carrying out scuff test and the test of dry-cleaning property with same method of embodiment A-1 and same evaluation method.The table 3 that the results are shown in scuff test and the test of dry-cleaning property.

The mensuration of (5) ejection stability

Use the black liquid of embodiment A-8, by spraying the mensuration of stability with same method of embodiment A-1 and same evaluation method.The measurement result of ejection stability is shown in table 3.

(reference example A-7)

Among the reference example A-7,, similarly carry out the preparation of black liquid with embodiment A-5 and estimate except the molecular weight of the high molecular particle that will be in the embodiment A-5 adds be changed to 90000 and 1100000.With molecular weight be 90000 latex as latex AK (EM-AK), be that 1100000 latex is as latex AL (EM-AL) with molecular weight.Black liquid composition is shown in table 4.Scuff test, the test of dry-cleaning property and ejection stability test and embodiment A-5 are similarly carried out.Show the result in table 3.The mensuration of the particle diameter of high molecular particle and embodiment A-1 similarly carried out.

(reference example A-8)

In reference example A-8, except with in the embodiment A-6 as 1,1 of 2-alkylene glycol, the 2-hexylene glycol is transformed to outside the glycerine, similarly prepares black liquid with embodiment A-6 and estimates.Black liquid composition is shown in table 4.Scuff test, the test of dry-cleaning property and ejection stability test and embodiment A-5 are similarly carried out.Show the result in table 3.

(reference example A-9)

In reference example A-9,, similarly prepare black liquid with embodiment A-7 and estimate except being that tensio-active agent and alkynol are that tensio-active agent is transformed to the glycerine at the alkyne diol in the embodiment A-7.Black liquid composition is shown in table 4.Scuff test, the test of dry-cleaning property and ejection stability test and embodiment A-5 are similarly carried out, and show the result in table 3.

(reference example A-10)

In reference example A-10, the amount of the high molecular particle that is added in making embodiment A-8 to be to be calculated as pigment ratio 80% and 50%, similarly prepares black liquid with embodiment A-8 and estimates.Black liquid composition is shown in table 4.Scuff test, the test of dry-cleaning property and ejection stability test and embodiment A-5 are similarly carried out, and show the result in table 3.

(reference example A-11～15)

In reference example A-11～15, except making at the sample that carries out full version lettering on the cotton and in 5 minutes condition of 150 ℃ of following heat treated in the embodiment A-6 carried out various changes, handling, similarly carry out with embodiment A-6, estimate erasibility.For with embodiment A-6 relatively, the example that will carry out various changes to condition is A-11～15 as a reference example, show the result in table 5.

The result of the erasibility in table 3 embodiment A-5～8, reference example A-7～10, dry-cleaning property, ejection stability

The unit of Tg is ℃, and particle diameter calculates with the median size of pigment, and its unit is nm, and the unit of acid number is mgKOH/g.

Molecular weight in the table 3 is * 10 ⁵

% with the relative pigment of high molecular particle represents to pigment ratio.

Erasibility, dry-cleaning property are according to the metewand of JIS.

The black liquid of table 4 embodiment A-5～8 and Comparative examples A-7～8 is formed (quality %)

Pigment and polymer concentration are represented with the solid branch that forms.

1,2-HD 1, the 2-hexylene glycol

1,2-PD 1, the 2-pentanediol

TEGmBE triglycol monobutyl ether

S-104 Surfynol 104 (a day letter chemistry system alkyne diol is a tensio-active agent)

S-465 Surfynol 465 (a day letter chemistry system alkyne diol is a tensio-active agent)

S-61 Surfynol 61 (a day letter chemistry system alkyne diol is a tensio-active agent)

The TMP TriMethylolPropane(TMP)

The TEG triglycol

The 2-P 2-Pyrrolidone

The TEA trolamine

Frictional property test-results in table 5 embodiment A-6 behind the change heating condition

(Embodiment B-1)

(1) preparation of pigment dispersion B1

Pigment dispersion B1 uses the system MONARCH 880 of U.S. Cabot Co.,Ltd as carbon black (Pigment black 7).The same method of utilization and Japanese patent laid-open 8-3498 communique can be distributed in the water sooty surface oxidation, becomes dispersion B1.Use Microtrac particle size distribution analyzer UPA250 (day machine dress system) to record particle diameter and be 110nm.

(2) preparation of high molecular particle

Ion exchanged water joined for 100 parts have dripping device, thermometer, the water-cooled reflux exchanger, in the reaction vessel of stirrer, while stirring in nitrogen atmosphere, add under 70 ℃ the condition as 0.2 part of the Potassium Persulphate of polymerization starter, 0.05 part of Sodium Lauryl Sulphate BP/USP is arranged in 7 parts of ion exchanged waters, splashing into to add under 70 ℃, 4 parts of glycidoxy acrylate, 15 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of castor-oil plant Chun oxazoline (methyl) acrylate, the monomer solution that 5 parts of butyl methacrylate and uncle's lauryl mercaptan are 0.02 part makes it reaction, makes material 1 time.In this 1 material, adding ammonium persulphate 10% solution stirs for 2 parts, add by 30 parts of ion exchanged waters while stirring down in 70 ℃ again, 0.2 part of lauryl potassium sulfate, 30 parts of ethyl propenoates, 25 parts of methyl acrylates, 6 parts of castor-oil plant Chun oxazoline acrylate, 5 parts in vinylformic acid, the reaction solution of 0.5 part of formation of uncle's lauryl mercaptan, make it carry out polyreaction, neutralize with sodium hydroxide then and transfer to pH to 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, with made high molecular particle aqueous dispersions as latex BA (EM-BA).After a part of taking out this high molecular particle aqueous dispersions made it drying, the vitrifying conversion temp of utilizing differential scanning calorimetry (Seiko-electronics system EXSTAR6000DSC) to record was-15 ℃.The vinylbenzene conversion molecular weight that uses the gel permeation chromatography (GPC) of the system L7100 of Hitachi Co., Ltd series, measures during as solvent with THF is 150000.In addition, the acid number that is recorded by volumetry is 20mgKOH/g.

(3) preparation of ink for inkjet recording liquid

Below the preferred group precedent in the ink for inkjet recording liquid is shown in Table 7.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the described vehicle composition of table 7 and make by the dispersion B1 that use utilizes described method to be prepared from.In addition, the water of the surplus in related embodiment, reference example and the comparative example of embodiments of the present invention B uses and has added the corrosive Mortopl Saden 240 (permachem asia corporate system) 0.05%, the corrosive benzotriazole 0.02% that is used to prevent the ink gun parts that are used for preventing black liquid respectively in ion exchanged water, be used to alleviate the water that EDTA (ethylenediamine tetraacetic acid (EDTA)) the 2Na salt 0.04% of influence of the metal ion of black liquid system forms.

(4) scuff test and the test of dry-cleaning property

Use the black liquid of Embodiment B-1, ink-jet printer uses the system PX-V600 of Seiko Epson Corp, carries out full version printing on cotton, makes sample.Under 150 ℃, carried out heat treated 5 minutes.Use of Tai Site (テ ス -) the Industry Co., Ltd formula friction stability experimental machine AB-301S that shakes, under loading 300g to this sample being wiped the determination test of 200 times friction stability.According to the JIS L0849 of Japanese Industrial Standards (JIS) of the situation of peeling off of confirming black liquid, adopt drying and moistening two standards to estimate.In addition, estimate the dry-cleaning test according to the B method of JIS L0860 equally.The table 6 that the results are shown in scuff test and dry-cleaning test.

The mensuration of (5) ejection stability

Ink-jet printer uses the system PX-V600 of Seiko Epson Corp, under 35 ℃, 35% atmosphere gas, XeroxP paper A4 in the zerox of Fuji corporate system opens, use Microsoft word, standard, MSP Gothic with middle literal size 11, ratio with 4000 word/pages or leaves, print 100 pages, estimate.To not have the AA that is designated as of lettering confusion fully, the A that is designated as of 1 place's lettering confusion will be arranged, the B that is designated as of 2～3 place's lettering confusions will be arranged, the C that is designated as of 4～5 place's lettering confusions will be arranged, the D that is designated as of the above lettering confusion in 6 places will be arranged, show the result in table 6.

(Embodiment B-2)

(1) preparation of pigment dispersion B2

At first, pigment dispersion B2 uses pigment Blue 15: 3 (CuPc pigment: Clariant system).With the reaction vessel that has stirrer, thermometer, return line and a dropping funnel with the nitrogen displacement after, add 75 parts of benzyl acrylates, 2 parts in vinylformic acid, 0.3 part of uncle's lauryl mercaptan, be heated to 70 ℃, in dropping funnel, add 1 part of 20 parts of 1 part of 5 parts of 15 parts in 150 parts of benzyl acrylates, vinylformic acid, butyl acrylates, uncle's lauryl mercaptan, methyl ethyl ketones preparing in addition and Sodium Persulfate, make the dispersed polymeres polymerization reaction take place with the limit of in reaction vessel, dripping, 4 hours limits.Then, in reaction vessel, add methyl ethyl ketone, prepare the dispersing polymer solution of 40% concentration.Take out the part of this polymkeric substance, make it drying after, the second-order transition temperature that utilizes differential scanning calorimetry (Seiko Epson EXSTAR6000DSC) to record is 40 ℃.

In addition, with the pigment Blue 15 of 40 parts of described dispersing polymer solutions and 30 parts: 3 mix for 30 parts with 100 parts of aqueous sodium hydroxide solutions, the methyl ethyl ketone of 0.1mol/L.Then, use ultra-high voltage homogenizer (the wild machinery system of Co., Ltd. China fir Altimizer HJP-25005),, disperse by 15 with 200MPa.Afterwards, be transferred in other containers, add 300 parts of ion exchanged waters, restir 1 hour.Afterwards, use rotary evaporator, whole methyl ethyl ketones and a part of water are boiled off, with the sodium hydroxide neutralization of 0.1mol/L, being adjusted to pH is 9.Then, with the membrane filtration of 0.3 μ m, obtaining pigment concentration with ion exchanged water adjustment is 15% pigment dispersion B2.The particle diameter that records with the method identical with Embodiment B-1 is 80nm.

(2) preparation of high molecular particle

Ion exchanged water is joined for 100 parts in the reaction vessel that has dripping device, thermometer, water-cooled reflux exchanger, stirrer, under nitrogen atmosphere, 70 ℃ condition, add as 0.2 part of the Potassium Persulphate of polymerization starter while stirring, in 7 parts of ion exchanged waters, splash under 70 ℃ add 0.05 part of Sodium Lauryl Sulphate BP/USP is arranged, the monomer solution of 0.02 part of 19 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of castor-oil plant Chun oxazoline (methyl) acrylate, 5 parts of butyl methacrylate and uncle's lauryl mercaptan, make it reaction, make material 1 time.In this 1 material, adding ammonium persulphate 10% solution stirs for 2 parts, add by 30 parts of ion exchanged waters while stirring down in 70 ℃ again, 0.2 part of lauryl potassium sulfate, 30 parts of ethyl propenoates, 25 parts of methyl acrylates, 10 parts of butyl acrylates, 6 parts of castor-oil plant Chun oxazoline acrylate, 5 parts in vinylformic acid, the reaction solution of 0.5 part of formation of uncle's lauryl mercaptan, after making it polyreaction, neutralizing with sodium hydroxide, to transfer to pH be 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, with made high molecular particle aqueous dispersions as latex BB (EM-BB).After a part of taking out this high molecular particle aqueous dispersions made it drying, the vitrifying conversion temp of utilizing differential scanning calorimetry (Seiko-electronics system EXSTAR6000DSC) to record was-17 ℃.By the molecular weight measured with the same method of Embodiment B-1 is 200000.In addition, the acid number that is recorded by volumetry is 20mgKOH/g.

(3) preparation of ink for inkjet recording liquid

Below, the preferred group in the ink for inkjet recording liquid is become to be illustrated in table 7.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the described vehicle composition of table 7 and similarly be prepared with Embodiment B-1 by the dispersion B2 that use utilizes described method to be prepared from.

(4) scuff test and the test of dry-cleaning property

Use to implement the black liquid of B-2, by carrying out scuff test and the test of dry-cleaning property with same method of Embodiment B-1 and same evaluation method.The table 6 that the results are shown in scuff test and the test of dry-cleaning property.

The mensuration of (5) ejection stability

Use the black liquid of Embodiment B-2,, the measurement result of ejection stability is shown in table 6 by the mensuration that sprays stability with same method of Embodiment B-1 and evaluation method.

(Embodiment B-3)

(1) preparation of pigment dispersion B3

At first, use pigment violet 19 (quinacridone pigment: the Clariant preparation) similarly make pigment dispersion B3 with pigment dispersion B2.Use the method identical to record particle diameter and be 90nm with Embodiment B-1.

(2) preparation of high molecular particle

Use the high molecular particle identical with Embodiment B-2.

(3) preparation of ink for inkjet recording liquid

Below, be illustrated in the table 7 preferred composition the in the ink for inkjet recording liquid.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the vehicle composition shown in the table 7 and similarly make and estimate with Embodiment B-1 by the dispersion B3 that use utilizes described method to be prepared from.

(4) scuff test and the test of dry-cleaning property

Use the black liquid of Embodiment B-3, and the same method of utilization and Embodiment B-1 and same evaluation method are carried out scuff test and the property dry-cleaned test.Result in scuff test shown in the table 6 and dry-cleaning test.

The mensuration of (5) ejection stability

Use the black liquid of Embodiment B-3, and same method of utilization and Embodiment B-1 and same evaluation method, carried out the stable mensuration of ejection.Measurement result in the stability of ejection shown in the table 6.

(Embodiment B-4)

(1) preparation of pigment dispersion B4

At first, use pigment Yellow 14 (azo pigment: the Clariant manufacturing) and with pigment dispersion B2 similarly make, with it as pigment dispersion B4.Use the method identical to record particle diameter and be 115nm with Embodiment B-1.

(2) preparation of high molecular particle

Use the high molecular particle identical with Embodiment B-2.

(3) preparation of ink for inkjet recording liquid

Below, the preferred group in the ink for inkjet recording liquid is become to be illustrated in table 7.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the vehicle composition shown in the table 7 and similarly be prepared and estimate with Embodiment B-1 by the dispersion B3 that use utilizes described method to be prepared from.

(4) scuff test and the test of dry-cleaning property

Utilize the black liquid of Embodiment B-4, and same method of utilization and Embodiment B-1 and same evaluation method, carried out scuff test and the test of dry-cleaning property.Result in scuff test shown in the table 6 and dry-cleaning test.

The mensuration of (5) ejection stability

Utilize the black liquid of Embodiment B-4, and same method of utilization and Embodiment B-1 and same evaluation method, carried out the mensuration of ejection stability.Measurement result in the stability of ejection shown in the table 6.

(comparative example B-1)

Comparative example B-1 is transformed to 45 parts of benzyl methacrylates with the total amount of the ethyl propenoate in the Embodiment B-1 (45 parts), in addition, similarly carry out with Embodiment B-1, and except using second-order transition temperature is 0 ℃ the high molecular particle, prepares black liquid in the same manner with Embodiment B-1 and estimates.The latex that utilizes this high molecular particle to make is called latex BC (EM-BC).Form at its black liquid shown in the table 7.Scuff test, the test of dry-cleaning property and ejection stability test have similarly been carried out with Embodiment B-1.In result shown in the table 6.

(comparative example B-2)

Comparative example B-2 changes to 10 parts of benzyl methacrylates with the total amount of the ethyl propenoate in the Embodiment B-2 (49 parts) instead of benzyl methacrylate and with 10 parts of butyl acrylate, in addition, similarly carry out with Embodiment B-2, the use second-order transition temperature is 10 ℃ a high molecular particle, in addition, prepare black liquid in the same manner with Embodiment B-2 and estimate.The latex that utilizes this high molecular particle to make is called latex BD (EM-BD).Form at its black liquid shown in the table 7.Scuff test, the test of dry-cleaning property and ejection stability test have similarly been carried out with Embodiment B-1.In result shown in the table 6.

(comparative example B-3)

Comparative example B-3 is in Embodiment B-3, and the particle diameter that makes pigment is the dispersion of 350nm and 45nm, in addition, prepares black liquid in the same manner with Embodiment B-3 and estimates.Utilize the method identical to measure particle diameter with Embodiment B-1.With particle diameter is that the dispersion of 350nm is called pigment dispersion B3A, is that the dispersion of 45nm is called pigment dispersion B3B with particle diameter.Form at its black liquid shown in the table 7.Scuff test, the test of dry-cleaning property and ejection stability test have similarly been carried out with Embodiment B-1.In result shown in the table 6.

(comparative example B-4)

Comparative example B-4 is in Embodiment B-4, changes the acid number of the high molecular particle that added into 120mgKOH/g and 150mgKOH/g, in addition, prepares black liquid in the same manner with Embodiment B-4 and estimates.The latex that utilizes acid number to make for the high molecular particle of 120mgKOH/g is called latex BE (EM-BE), the latex that utilizes acid number to make for the high molecular particle of 150mgKOH/g is made as latex BF (EM-BF).Form at its black liquid shown in the table 7.Scuff test, the test of dry-cleaning property and ejection stability test have similarly been carried out with Embodiment B-1.In result shown in the table 6.

(comparative example B-5)

Comparative example B-5 is in Embodiment B-2, does not use and have the compound that ethene is unsaturated group and oxazolinyl (castor-oil plant alcohol oxazoline (methyl) acrylate), in addition, prepares black liquid in the same manner with Embodiment B-2 and estimates.To use that need not to have ethene be unsaturated group with the high molecular particle of the compound of oxazolinyl (castor-oil plant Chun oxazoline (methyl) acrylate) and the latex made is made as latex BG (EM-BG) is formed at black liquid shown in the table 7.Scuff test, the test of dry-cleaning property and ejection stability test have similarly been carried out with Embodiment B-1.In result shown in the table 6.

(comparative example B-6)

Comparative example B-6 is in Embodiment B-3, does not use and have the compound that ethene is unsaturated group and oxazolinyl (castor-oil plant alcohol oxazoline (methyl) acrylate), in addition, prepares black liquid in the same manner with Embodiment B-3 and estimates.Form at black liquid shown in the table 7.Scuff test, the test of dry-cleaning property and ejection stability test have similarly been carried out with Embodiment B-1.In result shown in the table 6.

The result of the erasibility in table 6 Embodiment B-1～4, comparative example B-1～6, dry-cleaning property and ejection stability

The unit of Tg is ℃, and particle diameter calculates with the median size of pigment, and unit is nm, and the unit of acid number is mgKOH/g.

Erasibility, dry-cleaning property are based on the metewand of JIS.

The black liquid of table 7 Embodiment B-1～4, comparative example B-1～6 is formed (quality %)

Pigment and polymer concentration divide expression with solid formation.

1,2-HD 1, the 2-hexylene glycol

1,2-PD 1, the 2-pentanediol

TEGmBE triglycol monobutyl ether

S-104 Surfynol 104 (a day letter chemistry system alkyne diol is a tensio-active agent)

S-465 Surfynol 465 (a day letter chemistry system alkyne diol is a tensio-active agent)

S-61 Surfynol 61 (a day letter chemistry system alkyne diol is a tensio-active agent)

The TMP TriMethylolPropane(TMP)

The TEG triglycol

The 2-P 2-Pyrrolidone

The TEA trolamine

(Embodiment B-5)

(1) preparation of pigment dispersion B5

Pigment dispersion B5 uses the system MA100 of Mitsubishi Chemical Industrial Co., Ltd as carbon black (PBk7).The same method of utilization and Japanese patent laid-open 8-3498 communique makes the sooty surface oxidation that it can be distributed in the water, becomes dispersion B5.Use the method identical to record particle diameter and be 120nm with embodiment 1.

(2) preparation of high molecular particle

Ion exchanged water is joined for 100 parts in the reaction vessel that has dripping device, thermometer, water-cooled reflux exchanger, stirrer, under nitrogen atmosphere, 70 ℃ condition, add as 0.3 part of the Potassium Persulphate of polymerization starter while stirring, 0.05 part of Sodium Lauryl Sulphate BP/USP, 20 parts of ethyl propenoates are arranged in 7 parts of ion exchanged waters, splashing into to add under 70 ℃, the monomer solution that 15 parts of butyl acrylates, 6 parts in lauryl vinylformic acid, 5 parts of butyl methacrylate and uncle's lauryl mercaptan are 0.02 part makes it reaction, makes material 1 time.In this 1 material, adding ammonium persulphate 10% solution stirs for 2 parts, add by 30 parts of ion exchanged waters while stirring down in 70 ℃ again, 0.2 part of lauryl potassium sulfate, 6 parts of ethyl propenoates, 25 parts of butyl acrylates, 10 parts of lauryl acrylate, 6 parts of castor-oil plant Chun oxazoline methacrylic esters, 5 parts in vinylformic acid, the reaction solution of 0.5 part of formation of uncle's lauryl mercaptan, after making it polyreaction, neutralizing with sodium hydroxide, to transfer to pH be 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, with made high molecular particle aqueous dispersions as latex BI (EM-BI).After a part of taking out this high molecular particle aqueous dispersions made it drying, the vitrifying conversion temp of utilizing differential scanning calorimetry (Seiko-electronics system EXSTAR6000DSC) to record was-17 ℃.Using the molecular weight of the method mensuration identical with embodiment 1 is 180000.In addition, the acid number that is recorded by volumetry is 18mgKOH/g.

(3) preparation of ink for inkjet recording liquid

Below, the preferred group precedent in the ink for inkjet recording liquid is shown in Table 9.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the described vehicle composition of table 9 and similarly be prepared and estimate with Embodiment B-1 by the dispersion B5 that use utilizes described method to be prepared from.

(4) scuff test and the test of dry-cleaning property

Utilize the black liquid of Embodiment B-5, and same method and the same evaluation method of utilization and Embodiment B-1 scuff test and the test of dry-cleaning property have been carried out.Result in scuff test shown in the table 8 and dry-cleaning test.

The mensuration of (5) ejection stability

Utilize the black liquid of Embodiment B-5, and the same method of utilization and Embodiment B-1 and the same evaluation method mensuration of having carried out ejection stability.Measurement result in the stability of ejection shown in the table 8.

(Embodiment B-6)

(1) preparation of pigment dispersion B6

At first, pigment dispersion B6 uses pigment Blue 15: 3 (CuPc pigment: Clariant system).With the reaction vessel that has stirrer, thermometer, return line and a dropping funnel with the nitrogen displacement after, with 45 parts of vinylbenzene, 30 parts of poly(oxyethylene glycol) 400 acrylate, 10 parts of benzyl acrylates, 2 parts in vinylformic acid, 0.3 part of uncle's lauryl mercaptan, be heated to 70 ℃, in 150 parts of the vinylbenzene that will prepare in addition, 100 parts of poly(oxyethylene glycol) 400 acrylate, 15 parts in vinylformic acid, 5 parts of butyl acrylates, 1 part of uncle's lauryl mercaptan and 5 parts of adding dropping funnels of Sodium Persulfate, make the dispersed polymeres polymerization reaction take place while utilize 4 hours and splash into reaction vessel.Then, add entry to reaction vessel and make the dispersing polymer solution of 40% concentration.Take out after this high molecular part makes it drying, the vitrifying conversion temp of utilizing differential scanning type calorimeter (Seiko-electronics system EXSTAR6000DSC) to record is 45 ℃.

In addition, with 40 parts of the dispersing polymer solutions pigment Blue 15 with 30 parts: 3 mix for 100 parts with the aqueous sodium hydroxide solution of 0.1mol/L, use the Iger grinding machine that has utilized zirconium oxide bead to disperse 2 hours.Then, transfer to other container, add 300 parts of ion exchanged waters, further stirred 1 hour.Then, filter, make solid formation branch (dispersed polymeres and pigment Blue 15: 3) be 20% dispersion B6 with the filtering membrane of 0.3 μ m.Utilize the method identical with Embodiment B-1, measure particle diameter, the result is 100nm.Utilize the method determining molecular weight identical with Embodiment B-1, the result is 210000.

(2) preparation of high molecular particle

Ion exchanged water is joined for 100 parts in the reaction vessel that has dripping device, thermometer, water-cooled reflux exchanger, stirrer, under nitrogen atmosphere, 70 ℃ condition, add as 0.3 part of the Potassium Persulphate of polymerization starter while stirring, make it reaction in 7 parts of ion exchanged waters, splashing into the monomer solution that is added with 0.02 part of 0.05 part of Sodium Lauryl Sulphate BP/USP, 20 parts of ethyl propenoates, 25 parts of butyl acrylates, 6 parts of lauryl acrylate, 5 parts of butyl methacrylate and uncle's lauryl mercaptan under 70 ℃, make material 1 time.In this 1 material, adding ammonium persulphate 10% solution stirs for 2 parts, add by 30 parts of ion exchanged waters while stirring down in 70 ℃ again, 0.2 part of lauryl potassium sulfate, 20 parts of ethyl propenoates, 20 parts of butyl acrylates, 14 parts of lauryl acrylate, 6 parts of castor-oil plant Chun oxazoline methacrylic esters, 5 parts in vinylformic acid, the reaction solution of 0.5 part of formation of uncle's lauryl mercaptan, after making it polyreaction, neutralizing with sodium hydroxide, to transfer to pH be 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, with made high molecular particle aqueous dispersions as latex BJ (EM-BJ).After a part of taking out this high molecular particle aqueous dispersions made it drying, the vitrifying conversion temp of utilizing differential scanning calorimetry (Seiko-electronics system EXSTAR6000DSC) to record was-18 ℃.In addition, the acid number that is recorded by volumetry is 18mgKOH/g.

(3) preparation of ink for inkjet recording liquid

Below, the preferred group precedent in the ink for inkjet recording liquid is shown in Table 9.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the described vehicle composition of table 9 and similarly be prepared and estimate with Embodiment B-1 by the dispersion B6 that use utilizes described method to be prepared from.

(4) scuff test and the test of dry-cleaning property

Utilize the black liquid of Embodiment B-6, and same method and the same evaluation method of utilization and Embodiment B-1 scuff test and the test of dry-cleaning property have been carried out.Result in scuff test shown in the table 8 and dry-cleaning test.

The mensuration of (5) ejection stability

Utilize the black liquid of Embodiment B-6, and the same method of utilization and Embodiment B-1 and the same evaluation method mensuration of having carried out ejection stability.Measurement result in the stability of ejection shown in the table 8.

(Embodiment B-7)

(1) preparation of pigment dispersion B7

At first, use pigment violet 1 22 (dimethylquinacridone pigment: the Clariant manufacturing) and with pigment dispersion B6 similarly make pigment dispersion B7.Use the method identical to record particle diameter and be 80nm with Embodiment B-1.

(2) preparation of high molecular particle

Use the high molecular particle identical with Embodiment B-6.

(3) preparation of ink for inkjet recording liquid

Below, preferred group precedent in the ink for inkjet recording liquid is shown in Table 9.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the vehicle composition shown in the table 9 and similarly be prepared and estimate with Embodiment B-1 by the dispersion B7 that use utilizes described method to be prepared from.

(4) scuff test and the test of dry-cleaning property

Utilize the black liquid of Embodiment B-7, and same method and the same evaluation method of utilization and Embodiment B-1 scuff test and the test of dry-cleaning property have been carried out.Result in scuff test shown in the table 8 and dry-cleaning test.

The mensuration of (5) ejection stability

Utilize the black liquid of Embodiment B-7, and the same method of utilization and Embodiment B-1 and the same evaluation method mensuration of having carried out ejection stability.Measurement result in the stability of ejection shown in the table 8.

(Embodiment B-8)

(1) preparation of pigment dispersion B8

At first, (benzimidazolone is a disazo pigment: the Clariant manufacturing) and with pigment dispersion B6 similarly make pigment dispersion B8 to use Pigment Yellow 73 180.Use the method identical to record particle diameter and be 130nm with Embodiment B-1.

(2) preparation of high molecular particle

Use the high molecular particle identical with Embodiment B-6.

(3) preparation of ink for inkjet recording liquid

Below, preferred group precedent in the ink for inkjet recording liquid is shown in Table 9.In the preparation of ink for inkjet recording liquid of the present invention,, mix with the vehicle composition shown in the table 9 and similarly be prepared and estimate with Embodiment B-1 by the dispersion B8 that use utilizes described method to be prepared from.

(4) scuff test and the test of dry-cleaning property

Utilize the black liquid of Embodiment B-8, and same method and the same evaluation method of utilization and Embodiment B-1 scuff test and the test of dry-cleaning property have been carried out.Result in scuff test shown in the table 8 and dry-cleaning test.

The mensuration of (5) ejection stability

Utilize the black liquid of Embodiment B-8, and the same method of utilization and Embodiment B-1 and the same evaluation method mensuration of having carried out ejection stability.Measurement result in the stability of ejection shown in the table 8.

(reference example B-7)

Reference example B-7 changes into 90000 and 110000 except the molecular weight that makes the high molecular particle that is added in Embodiment B-5, prepares black liquid in the same manner with Embodiment B-5 and estimates.Molecular weight is made as 90000 latex and is made as latex BK (EM-BK), molecular weight is made as 110000 latex and is made as latex BL (EM-BL).Form at black liquid shown in the table 9.Scuff test, the test of dry-cleaning property and ejection stability test have similarly been carried out with Embodiment B-5.In result shown in the table 8.Utilize the method identical to carry out the mensuration of the particle diameter of high molecular particle with Embodiment B-1.

(reference example B-8)

Reference example B-8 is in Embodiment B-6, will be as 1, and 1 of 2-alkylene glycol, the 2-hexylene glycol is replaced into glycerine, in addition, prepares black liquid in the same manner with Embodiment B-6 and estimates.Form at black liquid shown in the table 9.Scuff test, the test of dry-cleaning property and ejection stability test have similarly been carried out with Embodiment B-5.In result shown in the table 8.

(reference example B-9)

Reference example B-9 is in Embodiment B-7, will be replaced into glycerine as the tensio-active agent of alkyne diol system and the tensio-active agent of alkynol system, in addition, prepares black liquid in the same manner with Embodiment B-7 and estimates.Form at black liquid shown in the table 9.Scuff test, the test of dry-cleaning property and ejection stability test have similarly been carried out with Embodiment B-5.In result shown in the table 8.

(reference example B-10)

Reference example B-10 is in Embodiment B-8, with the amount of the high molecular particle that added pigment ratio is calculated not 80% and 50%, in addition, prepare black liquid in the same manner with Embodiment B-8 and estimate.Form at black liquid shown in the table 9.Scuff test, the test of dry-cleaning property and ejection stability test have similarly been carried out with Embodiment B-5.In result shown in the table 8.

(reference example B-11～15)

Reference example B-11～15th is in Embodiment B-6, to making the sample that on cotton, carries out full version lettering and carrying out various variation back, processing in 5 minutes condition of 150 ℃ of following heat treated, in addition, prepare black liquid in the same manner and estimate scuff resistance with Embodiment B-6.In order to compare with embodiment 6, the example that will carry out various changes to condition is B-11～15 as a reference example, the results are shown in table 10.

The result of the erasibility in [table 8] Embodiment B-5～8, comparative example B-7～10, dry-cleaning property and ejection stability

The unit of Tg is ℃, and particle diameter calculates with the median size of pigment, and unit is nm, and the unit of acid number is mgKOH/g.

Molecular weight in the table 8 is * 10 ⁵

% with the relative pigment of high molecular particle represents to pigment ratio.

Erasibility, dry-cleaning property are according to the metewand of JIS.

The black liquid of [table 9] Embodiment B-5～8, reference example B-7～10 is formed (quality %)

Pigment and polymer concentration divide expression with solid formation.

The polymkeric substance emulsion of EPOCROS K-2020 Japan catalyst industry Zhi Han oxazoline

1,2-HD 1, the 2-hexylene glycol

1,2-PD 1, the 2-pentanediol

TEGmBE triglycol monobutyl ether

S-104 Surfynol 104 (a day letter chemistry system alkyne diol is a tensio-active agent)

S-465 Surfynol 465 (a day letter chemistry system alkyne diol is a tensio-active agent)

S-61 Surfynol 61 (a day letter chemistry system alkyne diol is a tensio-active agent)

The TMP TriMethylolPropane(TMP)

The TEG triglycol

The 2-P 2-Pyrrolidone

The TEA trolamine

Table 10 has changed the frictional property test-results behind the heating condition in Embodiment B-6

Claims (13)

1 one kinds of ink compositions is characterized in that, contain dispersion and high molecular particle, wherein,

Described dispersion be for can being dispersion below the above 300nm of 50nm to the median size in the water with colo(u)rant dispersion,

The second-order transition temperature of described high molecular particle for below-10 ℃, acid number is below the 100mgKOH/g, and use at least and have reactive compounds that ethene is unsaturated group and reactive group and alkyl (methyl) acrylate and/or cyclic alkyl (methyl) acrylate and synthesize as its constituent.

2. according to the described ink composition of claim 1, it is characterized in that,

Described reactive group is a blocked isocyanate Huo oxazolinyl.

3. ink composition according to claim 1 and 2 is characterized in that,

Described alkyl (methyl) acrylate and/or cyclic alkyl (methyl) acrylate are alkyl (methyl) acrylate of carbon number 1～24 and/or cyclic alkyl (methyl) acrylate of carbon number 3～24.

4. according to each described ink composition in the claim 1～3, it is characterized in that,

Described dispersion for do not use dispersion agent just can be dispersed in the water median size as below the above 300nm of 50nm from disperse black carbon.

5. according to each described ink composition in the claim 1～3, it is characterized in that,

Described dispersion be for can use polymkeric substance that the median size that pigment dyestuff is dispersed in the water is the dispersion below the above 300nm of 50nm,

The vinylbenzene conversion weight-average molecular weight that this polymkeric substance is surveyed by gel permeation chromatography (GPC) is more than 10000 below 200000.

6. according to each described ink composition in the claim 1～5, it is characterized in that,

The vinylbenzene conversion weight-average molecular weight that described high molecular particle is surveyed by gel permeation chromatography (GPC) is more than 100000 below 1000000.

7. according to each described ink composition in the claim 1～6, it is characterized in that,

Contain 1, the 2-alkylene glycol.

8. according to each described ink composition in the claim 1～7, it is characterized in that,

Containing alkyne diol is that tensio-active agent and/or alkynol are tensio-active agent.

9. according to each described ink composition in the claim 1～8, it is characterized in that,

The content (quality %) of the more described pigment of the content of described high molecular particle (quality %) is many.

10. an ink for inkjet recording liquid is characterized in that,

Described black liquid is each described ink composition in the claim 1～9.

11. an ink jet recording method is characterized in that having:

The described ink for inkjet recording liquid of claim 10 is printed onto operation on the cloth; And

This has been printed the operation of heat-treating below 200 ℃ more than 110 ℃ more than 1 minute that is distributed in of ink for inkjet recording liquid.

12. the manufacture method of an ink jet printing thing is characterized in that, has:

The described ink for inkjet recording liquid of claim 10 is printed onto operation on the cloth; And

This has been printed the operation of heat-treating below 200 ℃ more than 110 ℃ more than 1 minute that is distributed in of ink for inkjet recording liquid.

13. an ink jet printing thing is characterized in that,

Described ink jet printing thing is that the manufacture method by described ink jet recording method of claim 11 or the described ink jet printing thing of claim 12 obtains.