CN101525463A - Liquid composition for making pigment fixed, ink set, method for producing ink jet recorded matter on fabric and ink jet recorded matter on fabric - Google Patents
Liquid composition for making pigment fixed, ink set, method for producing ink jet recorded matter on fabric and ink jet recorded matter on fabric Download PDFInfo
- Publication number
- CN101525463A CN101525463A CNA2009101265013A CN200910126501A CN101525463A CN 101525463 A CN101525463 A CN 101525463A CN A2009101265013 A CNA2009101265013 A CN A2009101265013A CN 200910126501 A CN200910126501 A CN 200910126501A CN 101525463 A CN101525463 A CN 101525463A
- Authority
- CN
- China
- Prior art keywords
- pigment
- dispersion
- fabric
- stop bath
- recorded matter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Coloring (AREA)
Abstract
There are provided a liquid composition for making pigment fixed having a high resistance to rubbing and a good dry-cleanability; an ink set including the liquid composition for making pigment fixed and an ink composition excellent in terms of color intensity, discharge stability, and adhesiveness; and a method for producing ink-jet-recorded matter on a fabric having a high resistance to rubbing and good dry-cleanability using the liquid composition for making pigment fixed and the ink composition. The liquid composition for making pigment fixed according to the present invention contains at least a reactant and polymer fine particles synthesized from an alkyl (meth)acrylate and/or cyclic alkyl (meth)acrylate, the glass transition temperature and acid value of the liquid composition being equal to or lower than -10 DEG C. and equal to or lower than 100 mg KOH/g, respectively.
Description
Technical field
The present invention relates to scuff resistance and dry-cleaning property excellence the pigment stop bath, have this pigment stop bath and color developing, ejection stability, fixation performance excellence ink composition black liquid group and use the scuff resistance of this pigment stop bath and this ink composition and the manufacture method of the jet recorded matter on fabric of dry-cleaning property excellence and the jet recorded matter on fabric that obtains with this method.
Background technology
The black liquid that uses in the ink-vapor recording is as being recorded when printing on the paper of body and the cloth etc., require that having does not spread and sink in and ooze, drying property is good, can variously be recorded the uniform surface printing of body, characteristics such as adjacent color can not mix in the lettering of polychromes such as colored lettering system.
For described black liquid, particularly use the most of black liquid of pigment as colorant, people mainly study, by suppressing black liquid to being recorded the perviousness of body, suppress black liquid to being recorded the wetting of surface, guarantee the lettering quality by near black drop being stayed in be recorded the surface, and carry out practical application.But, in suppressing the wetting black liquid that is recorded body, because of being recorded the raw-material difference of body, it is big that the spreading and sinking in of black liquid oozed difference, particularly in the composition miscellaneous recycled writing paper of various paper, there are the following problems: ooze because of black liquid causes to spread and sink in to the difference of the wetting property of its each composition.In addition, also there are the following problems in this black liquid: the drying of print expends time in, and is adjacent color generation colour mixture (generation bleeding) in the lettering at polychromes such as colored letterings.In the print that has used pigment inks liquid, because pigment is being recorded the remained on surface of body, thereby the problem that exists the scuff resistance of print to descend.
In order to address the above problem, attempt to improve black liquid in the perviousness that is recorded on the body, inquire in black liquid, to add diethylene glycol monobutyl ether (with reference to patent documentation 1), in black liquid, add alkyne diol and be tensio-active agent Surfynol 465 (day letter chemistry system) (with reference to patent documentation 2) or in black liquid, add above-mentioned two kinds of materials (with reference to patent documentation 3) etc.
In addition, for the black liquid that has used pigment, usually be difficult in the perviousness that improves black liquid when guaranteeing colo(u)rant dispersion stability, so the range of choice of permeate agent is little, therefore, as the combination of glycol ethers and pigment, inquiring into the black liquid that the black liquid (with reference to patent documentation 4) that uses the triglycol monomethyl ether to form, the ethers (with reference to patent documentation 5) that makes spent glycol, glycol ether or triglycol in pigment etc. form in pigment.
As used for textiles China ink liquid, known have the black liquid (with reference to patent documentation 6) that uses dyestuff and the black liquid (with reference to patent documentation 7) relevant with tackiness agent.
In addition, about the print that has printed image etc. is carried out the technology that pad dyeing is handled, known have (with reference to patent documentations 8,9) such as the padding liquor that contains the regulation compound and pad dyeing methods.
Patent documentation 1: No. 5156675 specification sheets of United States Patent (USP)
Patent documentation 2: No. 5183502 specification sheets of United States Patent (USP)
Patent documentation 3: No. 5196056 specification sheets of United States Patent (USP)
Patent documentation 4: the Japanese Patent spy opens clear 56-147861 communique
Patent documentation 5: Japanese patent laid-open 9-111165 communique
Patent documentation 6: the Japanese Patent spy opens the 2007-515561 communique
Patent documentation 7: the Japanese Patent spy opens the 2007-126635 communique
Patent documentation 8: the Japanese Patent spy opens the 2005-281952 communique
Patent documentation 9: the Japanese Patent spy opens the 2004-149934 communique
But the scuff resistance of present padding liquor and dry-cleaning property are insufficient.In addition, in order to make the jet recorded matter on fabric of scuff resistance and dry-cleaning property excellence, study to the ink composition for ink-jet recording manufacturing that is fit to described jet recorded matter on fabric, color developing, ejection stability, fixation performance excellence and to the pigment stop bath of the most suitable this specific ink fluid composition.In addition, the manufacture method of the jet recorded matter on fabric of the scuff resistance that adopts above-mentioned ink composition for ink-jet recording and above-mentioned pigment stop bath and dry-cleaning property excellence is also studied.
From the viewpoint of ink composition for ink-jet recording, present water-based paint China ink liquid is when being used for textiles, and fixation performance is insufficient, and color depth and color developing are also insufficient.In addition, there are the following problems for present pigment dispersion: when existing tensio-active agent or glycol ethers etc. to have the material of hydrophilic portion and hydrophobic portion in the black liquid, then cause the desorption of dispersed polymeres easily from pigment, dispersed unstable, and storage stability ejection stability decreases.Usually aqueous ink oozes being recorded spreading and sinking in of body in order to reduce it, needs tensio-active agent or glycol ethers etc. to have the material of hydrophilic portion and hydrophobic portion.There are the following problems for the black liquid that does not use these materials: insufficient to the perviousness that is recorded body, easily cause that lettering image deterioration and the kind that is recorded body and the scope that can be used for the homogeneous lettering are restricted.
In addition, if (alkyne diol system and alkynol are tensio-active agent, two (three) glycol monobutyl ethers, (two) propylene glycol monobutyl ether or 1 to the additive that use black liquid of the present invention can contain in present pigment dispersion, 2-aklylene glycol or their mixture), then can not get secular storage stability, the variation of solvability again of China ink liquid, the problem on the top of the nozzle that therefore exists black liquid drying to become to stop up ink gun easily etc.
Summary of the invention
The present invention is the invention that is used to address the above problem, and its purpose is to provide the pigment stop bath (padding liquor) of a kind of scuff resistance and dry-cleaning property excellence; Black liquid group with this pigment stop bath and color developing, ejection stability, fixation performance excellence applicable to the ink composition of ink-vapor recording purposes; Use the manufacture method and the jet recorded matter on fabric of the jet recorded matter on fabric of the scuff resistance of this pigment stop bath and this ink composition and the property dry-cleaned excellence.
The present invention is as described below.
(1) a kind of pigment stop bath, it is characterized in that, contain high molecular particle and reagent, the second-order transition temperature of this high molecular particle below-10 ℃, acid number below 100mgKOH/g, and use (methyl) alkyl acrylate and/or (methyl) vinylformic acid cyclic alkyl ester to synthesize at least as its constituent.
According to above-mentioned (1) described pigment stop bath, it is characterized in that (2) above-mentioned reagent is at least a kind that selects from the group that polymkeric substance and poly-carbodiimide by blocked isocyanate, Han oxazoline constitute.
(3) according to above-mentioned (1) or (2) described pigment stop bath, it is characterized in that it is described (methyl) alkyl acrylate and/or (methyl) vinylformic acid cyclic alkyl ester more than the 70 quality % that described pigment stop bath contains with respect to described high molecular particle total amount.
According to each described pigment stop bath in above-mentioned (1)～(3), it is characterized in that (4) above-mentioned (methyl) alkyl acrylate and/or (methyl) vinylformic acid cyclic alkyl ester are (methyl) vinylformic acid C
1～C
24Alkyl ester and/or (methyl) vinylformic acid ring-type C
3～C
24Alkyl ester.
According to each described pigment stop bath in above-mentioned (1)～(4), it is characterized in that (5) the vinylbenzene conversion weight-average molecular weight that above-mentioned high molecular particle is recorded by gel permeation chromatography (GPC) is more than 100000 below 1000000.
(6) a kind of black liquid group is characterized in that, has each described pigment stop bath in ink composition and above-mentioned (1)～(5), wherein,
Above-mentioned ink composition contains can be with the dispersion of colo(u)rant dispersion in water.
According to above-mentioned (6) described black liquid group, it is characterized in that (7) median size of above-mentioned dispersion is below the above 300nm of 50nm.
(8) according to above-mentioned (7) described black liquid group, it is characterized in that, described dispersion for do not use dispersion agent just can be scattered in the water median size as below the above 300nm of 50nm from disperse black carbon.
According to above-mentioned (7) described black liquid group, it is characterized in that (9) described dispersion be for can use polymkeric substance that the median size that pigment dyestuff is scattered 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.
(10) according to each described black liquid group in above-mentioned (6)～(9), it is characterized in that above-mentioned ink composition contains 1, the 2-aklylene glycol.
(11) according to each described black liquid group in above-mentioned (6)～(10), it is characterized in that it is that tensio-active agent and/or alkynol are tensio-active agent that above-mentioned ink composition contains alkyne diol.
(12) according to each described black liquid group in above-mentioned (6)～(11), it is characterized in that the content of above-mentioned high molecular particle (quality %) is more than the content (quality %) of above-mentioned pigment.
(13) a kind of manufacture method of jet recorded matter on fabric is characterized in that, has:
To contain the ink composition of following dispersion carries out ink jet printing on cloth operation, described dispersion is can be with the dispersion of colo(u)rant dispersion in water;
This print be impregnated in the operation in each described pigment stop bath in the claim 1～5; With
With this dipping after print in the operation of thermal treatment below 200 ℃ more than 1 minute more than 110 ℃.
(14) a kind of manufacture method of jet recorded matter on fabric is characterized in that, has:
To contain the ink composition of following dispersion carries out ink jet printing on cloth operation, described dispersion is can be with the dispersion of colo(u)rant dispersion in water;
Utilize ink jet method each described pigment stop bath in the claim 1～5 to be coated the operation of this print; With
With this coating after print in the operation of thermal treatment below 200 ℃ more than 1 minute more than 110 ℃.
According to the manufacture method of above-mentioned (13) or (14) described jet recorded matter on fabric, it is characterized in that (15) median size of above-mentioned dispersion is below the above 300nm of 50nm.
(16) according to the manufacture method of above-mentioned (15) described jet recorded matter on fabric, it is characterized in that, described dispersion for do not use dispersion agent just can be scattered in the water median size as below the above 300nm of 50nm from disperse black carbon.
(17) according to the manufacture method of above-mentioned (15) described jet recorded matter on fabric, it is characterized in that, above-mentioned dispersion be for can use polymkeric substance that the median size that pigment dyestuff is scattered 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 recorded by gel permeation chromatography (GPC) is more than 10000 below 200000.
(18) according to the manufacture method of each described jet recorded matter on fabric in above-mentioned (13)～(17), it is characterized in that above-mentioned ink composition contains 1, the 2-aklylene glycol.
According to the manufacture method of each described jet recorded matter on fabric in above-mentioned (13)～(18), it is characterized in that (19) it is that tensio-active agent and/or alkynol are tensio-active agent that above-mentioned ink composition contains alkyne diol.
According to the manufacture method of each described jet recorded matter on fabric in above-mentioned (13)～(19), it is characterized in that (20) content of above-mentioned high molecular particle (quality %) is more than the content (quality %) of above-mentioned pigment.
(21) a kind of jet recorded matter on fabric is characterized in that, the manufacture method by each described jet recorded matter on fabric in above-mentioned (13)～(20) obtains.
Embodiment
[pigment stop bath]
Pigment stop bath of the present invention is characterised in that and contains high molecular particle and reagent, the second-order transition temperature of this high molecular particle is below-10 ℃, acid number below 100mgKOH/g, and use (methyl) alkyl acrylate and/or (methyl) vinylformic acid cyclic alkyl ester to synthesize at least as its constituent.According to this structure, the friction stability of jet recorded matter on fabric aspect metal to-metal contact and wet friction two improves, the raising of dry-cleaning property.
Below, each composition is described.
High molecular particle
The second-order transition temperature of high molecular particle is below-10 ℃.Take this, the fixation performance of the pigment of jet recorded matter on fabric improves.If surpass-10 ℃, then the fixation performance of pigment can descend gradually.Be preferably below-15 ℃, more preferably-20 ℃ below.
The acid number of high molecular particle is below the 100mgKOH/g.If surpass 100mgKOH/g, then the washing stability of jet recorded matter on fabric descends.Be preferably below the 50mgKOH/g, more preferably below the 30mgKOH/g.
The molecular weight of high molecular particle is preferably more than 100,000.More preferably more than 200,000.If less than 100,000, then the washing stability of jet recorded matter on fabric can descend.
In high molecular particle, contain (methyl) alkyl acrylate and/or (methyl) vinylformic acid cyclic alkyl ester as constituent, preferred (methyl) vinylformic acid C
1～C
24Alkyl ester and/or (methyl) vinylformic acid ring-type C
3～C
24Alkyl ester.As its example, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) ethyl acrylate, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) vinylformic acid Lauryl Ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid cetyl ester, (methyl) stearyl acrylate base ester, (methyl) vinylformic acid iso stearyl ester, (methyl) vinylformic acid tetramethyl-piperidyl ester, (methyl) vinylformic acid two ring pentyl esters, (methyl) vinylformic acid two cyclopentenes esters, dicyclopentenyl oxygen base (methyl) acrylate and (methyl) vinylformic acid docosyl ester etc.
The content of above-mentioned (methyl) alkyl acrylate and/or (methyl) vinylformic acid cyclic alkyl ester is preferably more than the 70 quality % of high molecular particle total amount.Because can further improve friction stability and the dry-cleaning property of jet recorded matter on fabric aspect metal to-metal contact and wet friction two like this.
The vinylbenzene conversion weight-average molecular weight that high molecular particle is recorded by gel permeation chromatography (GPC) is preferably more than 100000 below 1000000.When in this scope, the fixation performance of the pigment of jet recorded matter on fabric improves.
The median size of high molecular particle is measured with light scattering method.The particle diameter of the high molecular particle that is recorded by light scattering method is preferably below the above 500nm of 50nm, more preferably below the above 300nm of 60nm.If not enough 50nm, then the fixation performance of jet recorded matter on fabric descends, if surpass 500nm, then dispersion stabilization becomes unstable.In addition, when the pigment stop bath was carried out ink jet printing, it is unstable that the ejection of ink gun becomes easily.
Reagent
The present invention's so-called " reagent " is meant, have at least 1 above reactive group, also can have the compound of a plurality of reactive groups, it is by suitable processing such as thermal treatments, the functional group reactions that functional group's (for example hydroxyl that contains in the Mierocrystalline cellulose) that can be had with cloth, the functional group that high molecular particle had or dispersion (resin etc.) have.In addition, in the presence of suitable reaction initiator, reagent also can use the cross-linked compound with the material reaction that constitutes above-mentioned pigment dispersing agent, high molecular particle, cloth etc.In addition, reagent also comprise blocked isocyanate for example etc. and so on separately for inertia but wait the activatory compound through 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 order to be used for used for textiles ink-vapor recording purposes, preferably contain in the pigment stop bath of the present invention from by at least a kind that selects in the group that constitutes the polymkeric substance of blocked isocyanate, Han oxazoline and the poly-carbodiimide as reagent.
Blocked isocyanate
The preferred polymeric polyisocyanate of blocked isocyanate and be water-based emulsion.As its example, for example commercially available Xin Zhong village chemistry that has is made NKLinkerBX, the made Off イ of loose well pigment chemical industry Network サ one FX コ Application Network etc.In addition, also can open the method described in the 2007-45867 communique with the Japanese Patent spy makes.
The polymkeric substance of Han oxazoline
The polymkeric substance of Han oxazoline is preferably formed the form of water-based emulsion or the form of water-soluble polymers.For example, EPOCROSK-2010, EPOCROS K-2020, EPOCROS K-2030, EPOCROS WS-500, EPOCROS WS-700 etc. are made in commercially available have Xin Zhong village chemistry system NKLinkerFX, the industry of Japanese catalyzer.
Poly-carbodiimide
Above-mentioned poly-carbodiimide is preferably formed the form of water-based emulsion or the form of water-soluble polymers.As its example, for example commercially available SV-02, V-02, V-02-L2, V-04, E-01 and E-02 etc. that the Carbodilite that spins clearly day is arranged.Be somebody's turn to do the carbodiimide of poly-carbodiimide and the reaction of carboxyl and under acidity or high temperature, take place easily, therefore, under the state of pigment stop bath, be necessary for alkalescence from the viewpoint of storage stability.As the alkali that adds in the pigment stop bath, preferred ammonia has volatile alkali like this, also can be the organic amine of trolamine, tri-isopropanolamine and so on.PH is preferably more than 8 below 11.More preferably more than 8.5 below 10.The molecular weight of above-mentioned poly-carbodiimide is preferably more than 3000 below 100000.If less than 3000, then the storage stability of pigment stop bath descends.If surpass 100000, then the reaction of carbodiimide and carboxyl is difficult to carry out.More preferably more than 5000 below 30000.
Other compositions
As mentioned above, in the manufacture method of jet recorded matter on fabric of the present invention, contain by printings such as ink jet printings on the cloth can ink composition with the dispersion of colo(u)rant dispersion in water after, when (I) impregnated in this print the pigment stop bath or (II) during by ink jet method coating pigment stop bath etc., use pigment stop bath of the present invention on this print.
Pigment stop bath of the present invention except that above-mentioned must composition, can also preferably contain contain in the ink composition for ink-jet recording described later 1,2-aklylene glycol and glycol ethers, alkyne diol are that tensio-active agent and/or alkynol are tensio-active agent etc.
[black liquid group]
Black liquid group of the present invention is characterised in that it is the black liquid group with ink composition and above-mentioned pigment stop bath, and above-mentioned ink composition contains can be with the dispersion of colo(u)rant dispersion in water.
Below, each composition of ink composition is described.The ink composition of following explanation can be preferably used as ink composition for ink-jet recording.
Pigment dispersion
The median size of pigment dispersion is measured with light scattering method.The median size of pigment dispersion is as if not enough 50nm, and then the color developing of print, jet recorded matter on fabric can descend.In addition, if surpass 300nm, then fixation performance can descend.More preferably 70nm～230nm, more preferably 80nm～130nm.
As pigment dispersion, preferably do not use dispersion agent just can be scattered in the water median size as below the above 300nm of 50nm from disperse black carbon.Should be by using from disperse black carbon, the color developing of jet recorded matter on fabric improves.Have carbon blacksurface with the method for oxidations such as ozone, clorox etc. as not using dispersion agent just can be scattered in method in the water.Described median size from the disperse black carbon dispersion is preferably 50nm～150nm.If not enough 50nm then is difficult to obtain color developing.If surpass 150nm, then fixation performance can descend.Further preferred particle diameter is 70nm～130nm, more preferably 80nm～120nm.
As pigment dispersion, preferably comprise: can use polymkeric substance that the median size that pigment dyestuff is scattered in the water is the dispersion below the above 300nm of 50nm, wherein, the vinylbenzene conversion weight-average molecular weight that recorded by gel permeation chromatography (GPC) of described polymkeric substance is more than 10000 below 200000.Take this, the fixation performance of the pigment of jet recorded matter on fabric improves, and pigment inks liquid self memory stability also improves.In addition, except that above-mentioned polymkeric substance,, also can add the polymkeric substance of water dispersible or water-soluble or tensio-active agent as dispersion stabilizer in order in black liquid, pigment dispersion stably to be disperseed.Above-mentioned polymkeric substance is preferably served as reasons polymkeric substance that (methyl) acrylate and (methyl) acrylic acid copolymer obtain as its constituent more than at least 70 quality %.Because make dispersion stabilization good like this.
About pigment, as black ink liquid pigment, carbon black (C.I. Pigment black 7) classes such as preferred especially furnace treated black, dim, Shawinigan black, thermally oxidized black also can be used metal species, nigrosine pigment dyestuffs such as (C.I. Pigment blacks 1) such as copper oxide, ferriferous oxide (C.I. Pigment black 11), titanium oxide.
As color ink liquid pigment, (bright strong day red can to 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; Brilliant Fast Scarlet), 23,31,38,48:2 (permanent bordeaux 2B (Ba)), 48:2 (permanent bordeaux 2B (Ca)), 48:3 (permanent bordeaux 2B (Sr)), 48:4 (permanent bordeaux 2B (Mn)), 49:1,52:2,53:1,57:1 (gorgeous fuchsin 6B), 60:1,63:1,63:2,64:1,81 (rhodamine 6G color lakes), 83,88,101 (red iron oxides), 104,105,106,108 (cadmium reds), 112,114,122 (quinacridone magentas), 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, the various pigment that 36 grades and so on are used as colorant.
In addition, above-mentioned pigment can use dispersion machine to disperse, and as dispersion machine, can use commercially available various dispersion machines.From polluting few viewpoint, preferred non-medium disperses.As object lesson, can enumerate wet type airflow milling (jet mill) (Ji Nasi (ジ-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 Mechanology Inc. of China fir) and Microfluidizer (Microfluidics company) etc.
The addition of pigment is preferably 0.5 quality %～30 quality % (following also abbreviate as sometimes " % "), more preferably 1.0 quality %～15 quality %.If addition less than 0.5 quality %, then can't guarantee lettering concentration, if addition surpasses 30 quality %, then the viscosity of black liquid increases or structural viscosity occurs in viscosity characteristics, thereby has the trend of ejection bad stability of the black liquid of ink gun.
1, the 2-aklylene glycol
Black liquid of the present invention preferably contains 1, the 2-aklylene glycol.By using 1, the 2-aklylene glycol, minimizing is oozed in spreading and sinking in of print, jet recorded matter on fabric, and press quality improves.As 1, the example of 2-aklylene glycol, preferred 1,2-hexylene glycol, 1,2-pentanediol, 4-methyl isophthalic acid, carbonatomss such as 2-pentanediol be 5 or 61, the 2-aklylene glycol.Wherein, preferred carbonatoms be 61,2-hexylene glycol and 4-methyl isophthalic acid, 2-pentanediol.In addition, 1, the addition of 2-aklylene glycol is preferably 0.3 quality %～30 quality %, more preferably 0.5 quality %～10 quality %.
Glycol ethers
Black liquid of the present invention preferably contains glycol ethers.Because can reduce spreading and sinking in of print, jet recorded matter on fabric like this oozes.As glycol ethers, preferred use be selected from diethylene glycol monobutyl ether, triglycol monobutyl ether, propylene glycol monobutyl ether and the dipropylene glycol monobutyl ether more than a kind or 2 kinds.In addition, the addition of glycol ethers is preferably 0.1 quality %～20 quality %, more preferably 0.5 quality %～10 quality %.
Alkyne diol is that tensio-active agent and/or alkynol are tensio-active agent
It is that tensio-active agent and/or alkynol are tensio-active agent that black liquid of the present invention preferably contains alkyne diol.By using alkyne diol is that tensio-active agent and/or alkynol are tensio-active agent, can further reduce to spread and sink in and ooze, and improves press quality.Their interpolation improves the drying property of lettering, can carry out high speed printing.
As alkyne diol is that tensio-active agent and/or alkynol are tensio-active agent, be preferably selected from 2,4,7,9-tetramethyl--5-decine-4,7-glycol and 2,4,7,9-tetramethyl--5-decine-4, the oxirane affixture, 2 of 7-glycol, 4-dimethyl-5-decine-4-alcohol and 2, in the oxirane affixture of 4-dimethyl-5-decine-4-alcohol more than a kind.As their example, E series such as Olfine 104 series of free gasification worker (Britain) company that can obtain, Olfine E1010, day letter chemistry system Surfynol465 or Surfynol 61 etc.
In the present invention, by using from by above-mentioned 1,2-aklylene glycol, above-mentioned alkyne diol be tensio-active agent and/or alkynol be select in the group that constitutes of tensio-active agent, above-mentioned glycol ethers more than a kind or 2 kinds, can further reduce to spread and sink in and ooze.
In the black liquid group of the present invention, the content (quality %) of the above-mentioned pigment that above-mentioned high molecular particle that the preferred pigments stop bath contains and the total content of above-mentioned reagent (quality %) contain more than ink composition.The content (quality %) of the above-mentioned pigment that the content (quality %) of the above-mentioned high molecular particle that special preferred pigments stop bath contains contains more than ink composition.Take this, the fixation performance of the pigment of jet recorded matter on fabric improves.
In ink composition of the present invention, in order to ensure its shelf-stability, stably spray black liquid, improve to stop up or prevent black liquid deterioration etc., can also suitably add wetting Agent for Printing Inks, solubility promoter, infiltration control agent, viscosity modifier, pH regulator agent, solubility promoter, antioxidant, sanitas, mould inhibitor, anticorrosive agent, be used to catch disperseing the various additives such as inner complex of influential metal ion from ink gun.
[manufacture method of jet recorded matter on fabric]
The manufacture method of jet recorded matter on fabric of the present invention is characterised in that to have: will contain the ink composition of following dispersion carries out ink jet printing on cloth operation, described dispersion is can be with the dispersion of colo(u)rant dispersion in water; This print be impregnated in operation in the aforesaid pigment stop bath; With
With this coating after print in the operation of thermal treatment below 200 ℃ more than 1 minute more than 110 ℃.
In addition, the manufacture method of jet recorded matter on fabric of the present invention is characterised in that to have: will contain the ink composition of following dispersion carries out ink jet printing on cloth operation, described dispersion is can be with the dispersion of colo(u)rant dispersion in water; Utilize ink jet method the above-mentioned pigment stop bath of putting down in writing to be coated the operation of this print; With will be coated with after print in the operation of thermal treatment below 200 ℃ more than 1 minute more than 110 ℃.
Ink composition and pigment stop bath are as mentioned above.
If 110 ℃ of the Heating temperature less thaies in heat treatment step, then the fixation performance of jet recorded matter on fabric can not improve.If surpass 200 ℃, then cloth, pigment, polymkeric substance etc. self can deterioration.Heating temperature is preferably more than 120 ℃ below 170 ℃.In addition, need more than 1 minute heat-up time.If less than 1 minute, then the reaction of reagents such as the polymkeric substance of the blocked isocyanate, Han oxazoline that contains of pigment stop bath or poly-carbodiimide can not fully be carried out.Be preferably more than 2 minutes.
In addition, between above-mentioned ink jet printing operation and dipping operation or painting process, preferably add water or contain the operation that the water of tensio-active agent washs print.By described washing, can the photographic fixing of high molecular particle on cloth be become firmly from the water soluble component the printing logistics flush away China ink liquid, can further improve the scuff resistance of jet recorded matter on fabric.
On cloth during the printing ink fluid composition, preferably by adopting method piezoelectric element and so on, that do not cause the electrostriction element of heating to spray this China ink liquid.This is that it is unstable that ejection becomes easily because under the first-class situation that causes heating of for example temperature-sensitive, the polymkeric substance that uses in the dispersing of pigments in the high molecular particle in the pigment stop bath, the black liquid etc. can go bad.In the manufacturing of jet recorded matter on fabric and so on this operation, require preferably can not cause the shower nozzle of heating under the situation of a large amount of black liquid of long-term ejection.
[jet recorded matter on fabric]
Jet recorded matter on fabric of the present invention obtains by the manufacture method of above-mentioned jet recorded matter on fabric.
Below, be described more specifically the present invention by embodiment etc.In addition, the invention is not restricted to described embodiment.In addition, " part ", " % " during each of following embodiment formed represent " mass parts ", " quality % " respectively.
[embodiment]
(embodiment A-1)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion A1 that use is made by following method mixes with the vehicle shown in the table 2 (vehicle) composition, prepares ink for inkjet recording liquid.In addition, in " ion exchanged water (surplus) " in the black liquid of the present embodiment in present embodiment A and other embodiment, comparative example and reference example, contain 0.05% Mortopl Saden (ト Star プ サ イ De) 240 (the PermachemAsia corporate systems), 0.02% that are used for preventing black corrosion and be used to prevent that ink gun parts corrosive benzotriazole and 0.04% is used to reduce EDTA (ethylenediamine tetraacetic acid (EDTA)) the 2Na salt of the influence of black liquid metal ion.
The making of pigment dispersion A1
Pigment dispersion A1 adopts the system MONARCH 880 of U.S. Cabot Co.,Ltd as carbon black (Pigment black 7).Make the sooty surface oxidation and can be scattered in the water with the method identical, become dispersion A1 with Japanese patent laid-open 8-3498 communique.Measure particle diameter with Microtrac particle size distribution device UPA250 (day machine dress system), the result is 110nm.
(2) preparation of pigment stop bath
The high molecular particle aqueous dispersions (latex A A) that use is made by following method mixes with the vehicle composition shown in the table 3 that contains blocked isocyanate (Xin Zhong village chemistry system NKLinkerBX), prepares the pigment stop bath.In addition, in " ion exchanged water (surplus) " in this pigment stop bath in present embodiment A and the pigment stop bath of other embodiment, comparative example and reference example, contain 0.05% Mortopl Saden (ト Star プ サ イ De) 240 (the Permachem Asia corporate systems), 0.02% that are used for preventing black corrosion and be used to prevent that ink gun parts corrosive benzotriazole and 0.04% is used to reduce EDTA (ethylenediamine tetraacetic acid (EDTA)) the 2Na salt of the influence of black liquid metal ion.
The making of high molecular particle
In the reaction vessel that possesses Dropping feeder, thermometer, water-cooled reflux exchanger, stirrer, add 100 parts of ion exchanged waters, in nitrogen atmosphere gas, add 0.2 part of polymerization starter Potassium Persulphate down while stirring in 70 ℃, drip down the monomer solution that in 7 parts of ion exchanged waters, adds 0.05 part of Sodium Lauryl Sulphate BP/USP, 4 parts of glycidoxy acrylate, 15 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of tetrahydrofurfuryl acrylates, 5 parts of butyl methacrylate and 0.02 part of uncle's lauryl mercaptan and obtain at 70 ℃, make its reaction, make material 1 time.In this 1 material, add 2 parts of ammonium persulphate 10% solution and stirring, under 70 ℃, add while stirring then by 30 parts of ion exchanged waters, 0.2 part of lauryl potassium sulfate, 30 parts of ethyl propenoates, 25 parts of methyl acrylates, 6 parts of butyl acrylates, 5 parts in vinylformic acid, 0.5 part of reaction solution that forms of uncle's lauryl mercaptan, after carrying out polyreaction, neutralize with sodium hydroxide, making pH is 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, as latex A A (EM-AA).Get the part of this high molecular particle aqueous dispersions and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is-15 ℃.Using the gel permeation chromatography (GPC) of system L7100 system of Hitachi Co., Ltd, is that solvent is measured with THF, and the vinylbenzene conversion molecular weight that obtains is 150000.In addition, the acid number that records with volumetry is 20mgKOH/g.
(3) manufacture method of jet recorded matter on fabric
Adopt above-mentioned black liquid, use the system PX-V600 of Seiko Epson Corp, be produced on the print that full version lettering obtains on the cotton as ink-jet printer.Then, on this print, use identical printer that above-mentioned pigment stop bath is carried out full version lettering,, obtain the jet recorded matter on fabric sample 150 ℃ of following heat treated 5 minutes.
(4) scuff resistance test and the test of dry-cleaning property
Under the 300g load, smear and state sample (jet recorded matter on fabric) 200 times with of Tai Site (テ ス -) the Industry Co., Ltd formula friction stability trier AB-301S that shakes, estimate the friction stability.According to JIS (JIS) the JIS L0849 that confirms black liquid dropping situations, estimate by dry and moistening two standards.Similarly the dry-cleaning test is estimated with the B method of JIS L0860.The result of scuff resistance test and dry-cleaning test is as shown in table 1.
The mensuration of (5) ejection stability
Use the system PX-V600 of Seiko Epson Corp as ink-jet printer, use above-mentioned ink composition for ink-jet recording, under 35 ℃, 35% atmosphere gas, on the corporate system Xerox P of Fuji-Xerox paper A4, under Micosoft Word with No. 11 standard letters, MSP Gothic, in 100 pages of the ratio printings of 4000 word/pages or leaves and estimate.Not having the lettering entanglement fully is AA, and it is A that the lettering entanglement of 1 place is arranged, and it is B that 2 places～3 places lettering entanglement is arranged, and it is C that 4 places～5 places lettering entanglement is arranged, and it is D that the above lettering entanglement in 6 places is arranged.The result is as shown in table 1.
(embodiment A-2)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion A2 that use is made by following method mixes with the vehicle composition shown in the table 2, prepares ink for inkjet recording liquid.
The making of pigment dispersion A2
Pigment dispersion A2 adopts pigment Blue 15: 3 (copper phthalocyanines: Clariant system).After the reaction vessel that will possess stirrer, thermometer, return line and dropping funnel carries out the nitrogen displacement, add 75 parts of benzyl acrylates, 2 parts in vinylformic acid, 0.3 part of uncle's lauryl mercaptan, be heated to 70 ℃, pack in dropping funnel separately 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, methylethylketones preparing and Sodium Persulfate, ray flower were added drop-wise to that the limit makes dispersed polymeres carry out polyreaction in the reaction vessel in 4 hours.Then, in reaction vessel, add methylethylketone, make the dispersing polymer solution of 40% concentration.Get the part of this polymkeric substance and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is 40 ℃.
In addition, with 40 parts of the above-mentioned dispersing polymer solutions pigment Blue 15 with 30 parts: 3,100 parts of 0.1mol/L aqueous sodium hydroxide solutions, methylethylketone mix for 30 parts.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, transfer in other containers, add 300 parts of ion exchanged waters, and then stirred 1 hour.Heat up in a steamer whole methylethylketones and a part of water with rotatory evaporator, with the sodium hydroxide neutralization of 0.1mol/L, transferring to pH is 9.Then, filter, regulate, obtain pigment concentration and be 15% pigment dispersion A2 with ion exchanged water with the film filter of 0.3 μ m.Measure particle diameter with the method identical with embodiment A-1, the result is 80nm.
(2) preparation of pigment stop bath
The high molecular particle aqueous dispersions (latex A B) that use is made by following method mixes with the vehicle composition shown in the table 3 that contains blocked isocyanate (Xin Zhong village chemistry system NKLinkerBX), prepares the pigment stop bath.
The making of high molecular particle
In the reaction vessel that possesses Dropping feeder, thermometer, water-cooled reflux exchanger, stirrer, add 100 parts of ion exchanged waters, in nitrogen atmosphere gas, add 0.2 part of polymerization starter Potassium Persulphate down while stirring in 70 ℃, drip down the monomer solution that in 7 parts of ion exchanged waters, adds 0.05 part of Sodium Lauryl Sulphate BP/USP, 19 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of tetrahydrofurfuryl acrylates, 5 parts of butyl methacrylate and 0.02 part of uncle's lauryl mercaptan and obtain at 70 ℃, make its reaction, make 1 time material.In this 1 material, add 2 parts of ammonium persulphate 10% solution and stirring, under 70 ℃, add while stirring then by 30 parts of ion exchanged waters, 0.2 part of lauryl potassium sulfate, 30 parts of ethyl propenoates, 25 parts of methyl acrylates, 16 parts of butyl acrylates, 5 parts in vinylformic acid, 0.5 part of reaction solution that forms of uncle's lauryl mercaptan, after making it carry out polyreaction, neutralize with sodium hydroxide, making pH is 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, become latex A B (EM-AB).Take out the part of this high molecular particle aqueous dispersions and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is-17 ℃.With embodiment A-1 determining molecular weight similarly, the result is 200000.In addition, the acid number with titration measuring is 20mgKOH/g.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of embodiment A-2, use with the same method of embodiment A-1 and obtain the jet recorded matter on fabric sample.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with embodiment A-1.The result is as shown in table 1.
The mensuration of (5) ejection stability
Use the black liquid of embodiment A-2, use method identical and identical evaluation method to measure ejection stability with embodiment A-1.The measurement result of ejection stability is as shown in table 1.
(embodiment A-3)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion A3 that use is made by following method mixes with the vehicle composition shown in the table 2, prepares ink for inkjet recording liquid.
The making of pigment dispersion A3
Pigment dispersion A3 adopts pigment violet 19 (quinacridone pigment: Clariant system), and A2 similarly makes with pigment dispersion.In addition, use the method identical with embodiment A-1 to measure particle diameter, the result is 90nm.
(2) preparation of pigment stop bath
The latex A B that use is made in embodiment A-2 mixes with the vehicle composition shown in the table 3 that contains blocked isocyanate (Xin Zhong village chemistry system NKLinkerBX), prepares the pigment stop bath.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of embodiment A-3, use the method identical to obtain the jet recorded matter on fabric sample with embodiment A-1.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with embodiment A-1.The result is as shown in table 1.
The mensuration of (5) ejection stability
Use the black liquid of embodiment A-3, use method identical and identical evaluation method to measure ejection stability with embodiment A-1.The measurement result of ejection stability is as shown in table 1.
(embodiment A-4)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion A4 that use is made by following method mixes with the vehicle composition shown in the table 2, prepares ink for inkjet recording liquid.
The making of pigment dispersion A4
Pigment dispersion A4 adopts pigment Yellow 14 (azo pigment: Clariant system), and A2 similarly makes with pigment dispersion.Measure particle diameter with the method identical with embodiment A-1, the result is 115nm.
(2) preparation of pigment stop bath
The latex A B that use is made in embodiment A-2 mixes with the vehicle composition shown in the table 3 that contains blocked isocyanate (Xin Zhong village chemistry system NKLinkerBX), prepares the pigment stop bath.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of embodiment A-4, use the method identical to obtain the jet recorded matter on fabric sample with embodiment A-1.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with embodiment A-1.The result is as shown in table 1.
The mensuration of (5) ejection stability
Use the black liquid of embodiment A-4, use method identical and identical evaluation method to measure ejection stability with embodiment A-1.The measurement result of ejection stability is as shown in table 1.
(Comparative examples A-1)
In Comparative examples A-1, use by similarly to operate the second-order transition temperature of making especially be 0 ℃ high molecular particle except the ethyl propenoate total amount in the pigment stop bath of embodiment A-1 (45 parts) being changed into benzyl methacrylate 45, all prepare the pigment stop bath equally in addition with embodiment A-1.The emulsion of using this high molecular particle making is as latex A C (EM-AC).The pigment stop bath is formed as shown in table 3.In addition, the same pigment dispersion of use and embodiment A-1 prepares the black liquid of Comparative examples A-1.China ink liquid is formed as shown in table 2.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.The result is as shown in table 1.
(Comparative examples A-2)
In Comparative examples A-2, use by except the ethyl propenoate total amount in the pigment stop bath of embodiment A-2 (49 parts) is changed into benzyl methacrylate, changing 10 parts of butyl acrylate into benzyl methacrylate 10, similarly to operate the second-order transition temperature of making especially be 10 ℃ high molecular particle, all prepares the pigment stop bath equally with embodiment A-2 in addition.The emulsion of using this high molecular particle making is as latex A D (EM-AD).The pigment stop bath is formed as shown in table 3.In addition, the same pigment dispersion of use and embodiment A-2 prepares the black liquid of Comparative examples A-2.China ink liquid is formed as shown in table 2.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.The result is as shown in table 1.
(reference example A-3)
Reference example A-3 is in the black liquid of embodiment A-3, and making particle diameter is the pigment dispersion of 350nm and 45nm, in addition, prepares black liquid equally with embodiment A-3.Particle diameter adopts the method identical with embodiment A-3 to measure.The dispersion that with particle diameter is 350nm is as pigment dispersion A3A, and the dispersion that with particle diameter is 45nm is as pigment dispersion A3B.China ink liquid is formed as shown in table 2.In addition, the pigment stop bath of reference example A-3 adopts the pigment stop bath identical with embodiment A-3.The composition of pigment stop bath is as shown in table 3.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.The result is as shown in table 1.
(Comparative examples A-4)
In Comparative examples A-4, the acid number of the high molecular particle in the pigment stop bath that makes embodiment A-4 is 120mgKOH/g, the 150mgKOH/g, prepares the pigment stop bath equally with embodiment A-4.With the emulsion of using acid number to make as the high molecular particle of 120mgKOH/g as latex A E (EM-AE), with uses acid number as the emulsion of the high molecular particle making of 150mgKOH/g as latex A F (EM-AF).The pigment stop bath is formed as shown in table 3.In addition, the black liquid of Comparative examples A-4 adopts the black liquid identical with embodiment A-4.China ink liquid is formed as shown in table 2.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.The result is as shown in table 1.
(Comparative examples A-5)
In Comparative examples A-5, except in the pigment stop bath of embodiment A-2, not using blocked isocyanate (Xin Zhong village chemistry system NKLinkerBX), similarly prepare the pigment stop bath with embodiment A-2.The pigment stop bath is formed as shown in table 3.In addition, the black liquid of Comparative examples A-5 adopts the black liquid identical with embodiment A-2.China ink liquid is formed as shown in table 2.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.The result is as shown in table 1.
(Comparative examples A-6)
In Comparative examples A-6, except in the pigment stop bath of embodiment A-3, not using blocked isocyanate (Xin Zhong village chemistry system NKLinkerBX), similarly prepare the pigment stop bath with embodiment A-3.The pigment stop bath is formed as shown in table 3.In addition, the black liquid of Comparative examples A-6 adopts the black liquid identical with embodiment A-3.China ink liquid is formed as shown in table 2.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.The result is as shown in table 1.
[table 1]
The result of the scuff resistance among table 1 embodiment A-1～4, Comparative examples A-1～2,4～6, the reference example A-3, dry-cleaning property, ejection stability
The unit of Tg is ℃, and particle diameter is the median size of pigment, and unit is nm, and the unit of acid number is mgKOH/g.Scuff resistance, dry-cleaning property are abideed by the judgement criteria of JIS.
[table 2]
The black liquid of table 2 embodiment A-1～4, Comparative examples A-1～2,4～6, reference example A-3 is formed (quality %)
The concentration of pigment is represented with solids component.
1,2-HD 1,2-hexylene glycol
1,2-PD 1,2-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 alkynol is a tensio-active agent)
The TMP TriMethylolPropane(TMP)
The TEG triglycol
The 2-P 2-Pyrrolidone
The TEA trolamine
[table 3]
The pigment stop bath of table 3 embodiment A-1～4, Comparative examples A-1～2,4～6, reference example A-3 is formed (quality %)
Polymer concentration is represented with solids component.
NKLinkerBX Xin Zhong village chemistry system blocked isocyanate emulsion
1,2-HD 1,2-hexylene glycol
1,2-PD 1,2-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 alkynol 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 ink for inkjet recording liquid
The pigment dispersion A5 that use is made by following method mixes with the vehicle composition shown in the table 5, prepares ink for inkjet recording liquid.
The making of pigment dispersion A5
Pigment dispersion A5 adopts the system MA100 of Mitsubishi Chemical Industrial Co., Ltd as carbon black (PBk7).Make the carbon blacksurface oxidation and can be scattered in the water with the method identical, make dispersion A5 with Japanese patent laid-open 8-3498 communique.Measure particle diameter with the method identical with embodiment A-1, the result is 120nm.
(2) preparation of pigment stop bath
The high molecular particle aqueous dispersions (latex A I) that use is made by following method mixes with the vehicle composition shown in the table 6 that contains blocked isocyanate (Xin Zhong village chemistry system NKLinkerBX), prepares the pigment stop bath.
The making of high molecular particle
In the reaction vessel that possesses Dropping feeder, thermometer, water-cooled reflux exchanger, stirrer, add 100 parts of ion exchanged waters, in nitrogen atmosphere gas, add 0.3 part of polymerization starter Potassium Persulphate down while stirring in 70 ℃, drip down the monomer solution that in 7 parts of ion exchanged waters, adds 0.05 part of Sodium Lauryl Sulphate BP/USP, 20 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of vinylformic acid Lauryl Ester, 5 parts of butyl methacrylate and 0.02 part of uncle's lauryl mercaptan and obtain at 70 ℃, make its reaction, make 1 time material.In this 1 material, add 2 parts of ammonium persulphate 10% solution and stirring, under 70 ℃, add while stirring then by 30 parts of ion exchanged waters, 0.2 part of lauryl potassium sulfate, 30 parts of ethyl propenoates, 25 parts of butyl acrylates, 16 parts of vinylformic acid Lauryl Ester, 5 parts in vinylformic acid, 0.5 part of reaction solution that forms of uncle's lauryl mercaptan, after carrying out polyreaction, neutralize with sodium hydroxide, making pH is 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, as latex A I (EM-AI).Get the part of this high molecular particle aqueous dispersions and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is-19 ℃.With the method determining molecular weight identical with embodiment A-1, the result is 180000.In addition, the acid number with titration measuring is 18mgKOH/g.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of embodiment A-5, use with the same method of embodiment A-1 and obtain the jet recorded matter on fabric sample.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with embodiment A-1.The result is as shown in table 4.
The mensuration of (5) ejection stability
Use the black liquid of embodiment A-5, use method identical and identical evaluation method to measure ejection stability with embodiment A-1.The measurement result of ejection stability is as shown in table 4.
(embodiment A-6)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion A6 that use is made by following method mixes with the vehicle composition shown in the table 5, prepares ink for inkjet recording liquid.
The making of pigment dispersion A6
Pigment dispersion A6 adopts pigment Blue 15: 3 (copper phthalocyanines: Clariant system).After the reaction vessel that will possess stirrer, thermometer, return line and dropping funnel carries out the nitrogen displacement, add 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 ℃, pack in dropping funnel separately 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 and Sodium Persulfates, ray flower were added drop-wise to that the limit makes dispersed polymeres carry out polyreaction in the reaction vessel in 4 hours.Then, in reaction vessel, add water, make the dispersing polymer solution of 40% concentration.Get the part of this polymkeric substance and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is 45 ℃.
With 40 parts of above-mentioned dispersing polymer solutions and 30 parts of pigment Blue 15s: 3 (copper phthalocyanines: Clariant system), 0.1mol/L aqueous sodium hydroxide solution mix for 100 parts, use the Chinese mugwort loud, high-pitched sound mill (ア イ ガ-ミ Le) that adopts the zirconium pearl to disperse 2 hours.Afterwards, transfer in other containers, add 300 parts of ion exchanged waters, stirred then 1 hour.With the sodium hydroxide neutralization of 0.1mol/L, transferring to pH is 9.Then, filter, make solids component (dispersed polymeres and pigment Blue 15: 3) be 20% dispersion A6 with the film filter of 0.3 μ m.Measure particle diameter with the method identical with embodiment A-1, the result is 100nm.The measurement result of molecular weight is 210000.
(2) preparation of pigment stop bath
The high molecular particle aqueous dispersions (latex A J) that use is made by following method mixes with the vehicle composition shown in the table 6 that contains blocked isocyanate (Xin Zhong village chemistry system NKLinkerBX), prepares the pigment stop bath.
The making of high molecular particle
In the reaction vessel that possesses Dropping feeder, thermometer, water-cooled reflux exchanger, stirrer, add 100 parts of ion exchanged waters, in nitrogen atmosphere gas, add 0.3 part of polymerization starter Potassium Persulphate down while stirring in 70 ℃, drip down the monomer solution that in 7 parts of ion exchanged waters, adds 0.05 part of Sodium Lauryl Sulphate BP/USP, 20 parts of ethyl propenoates, 25 parts of butyl acrylates, 6 parts of vinylformic acid Lauryl Ester, 5 parts of butyl methacrylate and 0.02 part of uncle's lauryl mercaptan and obtain at 70 ℃, make its reaction, make 1 time material.In this 1 material, add 2 parts of ammonium persulphate 10% solution and stirring, under 70 ℃, add while stirring then by 30 parts of ion exchanged waters, 0.2 part of lauryl potassium sulfate, 20 parts of ethyl propenoates, 20 parts of butyl acrylates, 20 parts of vinylformic acid Lauryl Ester, 5 parts in vinylformic acid, 0.5 part of reaction solution that forms of uncle's lauryl mercaptan, after carrying out polyreaction, neutralize with sodium hydroxide, making pH is 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, as latex A J (EM-AJ).Get the part of this high molecular particle aqueous dispersions and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is-21 ℃.In addition, the acid number with titration measuring is 18mgKOH/g.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of embodiment A-6, use with the same method of embodiment A-1 and obtain the jet recorded matter on fabric sample.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with embodiment A-1.The result is as shown in table 4.
The mensuration of (5) ejection stability
Use the black liquid of embodiment A-6, use method identical and identical evaluation method to measure ejection stability with embodiment A-1.The measurement result of ejection stability is as shown in table 4.
(embodiment A-7)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion A7 that use is made by following method mixes with the vehicle composition shown in the table 5, prepares ink for inkjet recording liquid.
The making of pigment dispersion A7
Pigment dispersion A7 adopts pigment red 122, and (dimethylquinacridone pigment: Clariant system), A6 similarly makes with pigment dispersion.Measure particle diameter with the method identical with embodiment A-1, the result is 80nm.
(2) preparation of pigment stop bath
The latex A J that use is made in embodiment A-6 mixes with the vehicle composition shown in the table 6 that contains blocked isocyanate (Xin Zhong village chemistry system NKLinkerBX), prepares the pigment stop bath.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of embodiment A-7, use the method identical to obtain the jet recorded matter on fabric sample with embodiment A-1.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with embodiment A-1.The result is as shown in table 4.
The mensuration of (5) ejection stability
Use the black liquid of embodiment A-7, use method identical and identical evaluation method to measure ejection stability with embodiment A-1.The measurement result of ejection stability is as shown in table 4.
(embodiment A-8)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion A8 that use is made by following method mixes with the vehicle composition shown in the table 5, prepares ink for inkjet recording liquid.
The making of pigment dispersion A8
Pigment dispersion A8 adopts Pigment Yellow 73 180, and (benzimidazolone is a disazo pigment: Clariant system), A6 similarly makes with pigment dispersion.Measure particle diameter with the method identical with embodiment A-1, the result is 130nm.
(2) preparation of pigment stop bath
The latex A J that use is made in embodiment A-6 mixes with the vehicle composition shown in the table 6 that contains blocked isocyanate (Xin Zhong village chemistry system NKLinkerBX), prepares the pigment stop bath.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of embodiment A-8, use the method identical to obtain the jet recorded matter on fabric sample with embodiment A-1.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with embodiment A-1.The result is as shown in table 4.
The mensuration of (5) ejection stability
Use the black liquid of embodiment A-8, use method identical and identical evaluation method to measure ejection stability with embodiment A-1.The measurement result of ejection stability is as shown in table 4.
(reference example A-7)
In reference example A-7,, similarly prepare the pigment stop bath with embodiment A-5 except the molecular weight of the high molecular particle of the pigment stop bath that makes embodiment A-5 is 90000 and 1100000.With molecular weight be 90000 emulsion as latex A K (EM-AK), be that 1100000 emulsion is as latex A L (EM-AL) with molecular weight.The composition of pigment stop bath is as shown in table 6.In addition, use the black liquid of the pigment dispersion preparation reference example A-7 identical with embodiment A-5.China ink liquid is formed as shown in table 5.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.The result is as shown in table 4.
(reference example A-8)
In reference example A-8, except with in the embodiment A-6 as 1,1 of 2-aklylene glycol, the 2-hexylene glycol changes into outside the glycerine, similarly prepares black liquid and pigment stop bath with embodiment A-6.China ink liquid is formed as shown in table 5, and the pigment stop bath is formed as shown in table 6.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.The result is as shown in table 4.
(reference example A-9)
In reference example A-9,, similarly prepare black liquid and pigment stop bath with embodiment A-7 except being that tensio-active agent and alkynol are that tensio-active agent changes into the glycerine with the alkyne diol in the embodiment A-7.China ink liquid is formed as shown in table 5, and the pigment stop bath is formed as shown in table 6.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.The result is as shown in table 4.
(reference example A-10)
In reference example A-10,, similarly prepare ink composition and pigment stop bath with embodiment A-8 except the amount of the high molecular particle of the pigment stop bath in the embodiment A-8 ratio with respect to pigment is changed into 80%, 50%.Ink composition is as shown in table 5, and the pigment stop bath is formed as shown in table 6.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and embodiment A-1 are similarly carried out.The result is as shown in table 4.
(reference example A-11～15)
In reference example A-11～15, and be produced on the cotton sample that full version lettering obtains in the embodiment A-6 equally, except carrying out similarly estimating scuff resistance with embodiment A-6 various changes handle in 5 minutes condition of 150 ℃ of following heat treated.In order to compare with embodiment A-6, with the example of various condition changings A-11～15 as a reference example, the result is as shown in table 7.
[table 4]
The result of the scuff resistance in table 4 embodiment A-5～8, reference example A-7～10, dry-cleaning property, ejection stability
The unit of Tg is ℃, and particle diameter is the median size of pigment, and unit is nm, and the unit of acid number is mgKOH/g.
Molecular weight in the table 4 is * 10
5
Use % to represent to pigment ratio with respect to the high molecular particle of pigment.
Scuff resistance, dry-cleaning property are abideed by the judgement criteria of JIS.
[table 5]
The black liquid of table 5 embodiment A-5～8 and reference example A-7～10 is formed (quality %)
Pigment concentration is represented with solids component.
1,2-HD 1,2-hexylene glycol
1,2-PD 1,2-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 alkynol is a tensio-active agent)
The TMP TriMethylolPropane(TMP)
The TEG triglycol
The 2-P 2-Pyrrolidone
The TEA trolamine
[table 6]
The pigment stop bath of table 6 embodiment A-5～8 and reference example A-7～10 is formed (quality %)
Polymer concentration is represented with solids component.
NKLinkerBX Xin Zhong village chemistry system blocked isocyanate emulsion
1,2-HD 1,2-hexylene glycol
1,2-PD 1,2-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 alkynol is a tensio-active agent)
The TMP TriMethylolPropane(TMP)
The TEG triglycol
The 2-P 2-Pyrrolidone
The TEA trolamine
[table 7]
Frictional property test-results when changing heating condition in table 7 embodiment A-6
(Embodiment B-1)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion B1 that use is made by following method mixes with the vehicle composition shown in the table 9, prepares ink for inkjet recording liquid.In addition, in " ion exchanged water (surplus) " in the black liquid of the present embodiment in present embodiment B and other embodiment, comparative example and reference example, contain 0.05% Mortopl Saden (ト Star プ サ イ De) 240 (the Permachem Asia corporate systems), 0.02% that are used for preventing black corrosion and be used to prevent that ink gun parts corrosive benzotriazole and 0.04% is used to reduce EDTA (ethylenediamine tetraacetic acid (EDTA)) the 2Na salt of the influence of black liquid metal ion.
The making of pigment dispersion B1
Pigment dispersion B1 adopts the system MONARCH880 of U.S. Cabot Co.,Ltd as carbon black (Pigment black 7).Make the sooty surface oxidation and can be scattered in the water with the method identical, make dispersion B1 with Japanese patent laid-open 8-3498 communique.Measure particle diameter with Microtrac particle size distribution device UPA250 (day machine dress system), the result is 110nm.
(2) preparation of pigment stop bath
The high molecular particle aqueous dispersions (emulsion BA) that use is made by following method mixes with the vehicle composition shown in the table 10 of the polymkeric substance that contains oxazoline (Xin Zhong village chemistry system NKLinkerFX), prepares the pigment stop bath.In addition, in " ion exchanged water (surplus) " in this pigment stop bath in present embodiment B and the pigment stop bath of other embodiment, comparative example and reference example, contain 0.05% Mortopl Saden (ト Star プ サ イ De) 240 (the PermachemAsia corporate systems), 0.02% that are used for preventing black corrosion and be used to prevent that ink gun parts corrosive benzotriazole and 0.04% is used to reduce EDTA (ethylenediamine tetraacetic acid (EDTA)) the 2Na salt of the influence of black liquid metal ion.
The making of high molecular particle
In the reaction vessel that possesses Dropping feeder, thermometer, water-cooled reflux exchanger, stirrer, add 100 parts of ion exchanged waters, in nitrogen atmosphere gas, add 0.2 part of polymerization starter Potassium Persulphate down while stirring in 70 ℃, drip down the monomer solution that in 7 parts of ion exchanged waters, adds 0.05 part of Sodium Lauryl Sulphate BP/USP, 4 parts of glycidoxy acrylate, 15 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of tetrahydrofurfuryl acrylates, 5 parts of butyl methacrylate and 0.02 part of uncle's lauryl mercaptan and obtain at 70 ℃, make its reaction, make 1 time material.In this 1 material, add 2 parts of ammonium persulphate 10% solution and stirring, under 70 ℃, add while stirring then by 30 parts of ion exchanged waters, 0.2 part of lauryl potassium sulfate, 30 parts of ethyl propenoates, 25 parts of methyl acrylates, 6 parts of butyl acrylates, 5 parts in vinylformic acid, 0.5 part of reaction solution that forms of uncle's lauryl mercaptan, after carrying out polyreaction, neutralize with sodium hydroxide, making pH is 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, as emulsion BA (EM-BA).Get the part of this high molecular particle aqueous dispersions and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is-15 ℃.Using the gel permeation chromatography (GPC) of system L7100 system of Hitachi Co., Ltd, is that solvent is measured with THF, and the vinylbenzene conversion molecular weight that obtains is 150000.In addition, the acid number that records with volumetry is 20mgKOH/g.
(3) manufacture method of jet recorded matter on fabric
Adopt above-mentioned black liquid, use the system PX-V600 of Seiko Epson Corp, be produced on the print that full version lettering obtains on the cotton as ink-jet printer.Then, on this print, use identical printer that above-mentioned pigment stop bath is carried out full version lettering,, obtain the jet recorded matter on fabric sample 150 ℃ of following heat treated 5 minutes.
(4) scuff resistance test and the test of dry-cleaning property
Under the 300g load, smear and state sample (jet recorded matter on fabric) 200 times with of Tai Site (テ ス -) the Industry Co., Ltd formula friction stability trier AB-301S that shakes, estimate the friction stability.According to JIS (JIS) the JIS L0849 that confirms black liquid dropping situations, estimate by dry and moistening these two standards.Similarly the dry-cleaning test is estimated with the B method of JIS L0860.The result of scuff resistance test and dry-cleaning test is as shown in table 8.
The mensuration of (5) ejection stability
Use the system PX-V600 of Seiko Epson Corp as ink-jet printer, use above-mentioned ink composition for ink-jet recording, under 35 ℃, 35% atmosphere gas, on the corporate system Xerox P of Fuji-Xerox paper A4, under Micosoft Word with No. 11 standard letters, MSP Gothic, in 100 pages of the ratio printings of 4000 word/pages or leaves and estimate.Not having the lettering entanglement fully is AA, and it is A that the lettering entanglement of 1 place is arranged, and it is B that 2 places～3 places lettering entanglement is arranged, and it is C that 4 places～5 places lettering entanglement is arranged, and it is D that the above lettering entanglement in 6 places is arranged.The result is as shown in table 8.
(Embodiment B-2)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion B2 that use is made by following method mixes with the vehicle composition shown in the table 9, prepares ink for inkjet recording liquid.
The making of pigment dispersion B2
Pigment dispersion B2 adopts pigment Blue 15: 3 (copper phthalocyanines: Clariant system).After the reaction vessel that will possess stirrer, thermometer, return line and dropping funnel carries out the nitrogen displacement, add 75 parts of benzyl acrylates, 2 parts in vinylformic acid, 0.3 part of uncle's lauryl mercaptan, be heated to 70 ℃, pack in dropping funnel separately 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, methylethylketones preparing and Sodium Persulfate, ray flower were added drop-wise to that the limit makes dispersed polymeres carry out polyreaction in the reaction vessel in 4 hours.Then, in reaction vessel, add methylethylketone, make the dispersing polymer solution of 40% concentration.Get the part of this polymkeric substance and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is 40 ℃.
With 40 parts of above-mentioned dispersing polymer solutions and 30 parts of pigment Blue 15s: 3,100 parts of 0.1mol/L aqueous sodium hydroxide solutions, methylethylketone mix for 30 parts.Use ultra-high voltage homogenizer (the wild machinery system of Co., Ltd. China fir Altimizer HJP-25005) under 200MPa, to disperse then by (pass) 15.Afterwards, transfer in other containers, add 300 parts of ion exchanged waters, stirred then 1 hour.Heat up in a steamer whole methylethylketones and a part of water with rotatory evaporator, with the sodium hydroxide neutralization of 0.1mol/L, transferring to pH is 9.Then, filter, regulate, obtain pigment concentration and be 15% pigment dispersion B2 with ion exchanged water with the film filter of 0.3 μ m.Measure particle diameter with the method identical with Embodiment B-1, the result is 80nm.
(2) preparation of pigment stop bath
The high molecular particle aqueous dispersions (emulsion BB) that use is made by following method mixes with the vehicle composition shown in the table 10 of the polymkeric substance that contains oxazoline (Xin Zhong village chemistry system NKLinkerFX), prepares the pigment stop bath.
The making of high molecular particle
In the reaction vessel that possesses Dropping feeder, thermometer, water-cooled reflux exchanger, stirrer, add 100 parts of ion exchanged waters, in nitrogen atmosphere gas, add 0.2 part of polymerization starter Potassium Persulphate down while stirring in 70 ℃, drip down the monomer solution that in 7 parts of ion exchanged waters, adds 0.05 part of Sodium Lauryl Sulphate BP/USP, 19 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of tetrahydrofurfuryl acrylates, 5 parts of butyl methacrylate and 0.02 part of uncle's lauryl mercaptan and obtain at 70 ℃, make its reaction, make 1 time material.In this 1 material, add 2 parts of ammonium persulphate 10% solution and stirring, under 70 ℃, add while stirring then by 30 parts of ion exchanged waters, 0.2 part of lauryl potassium sulfate, 30 parts of ethyl propenoates, 25 parts of methyl acrylates, 16 parts of butyl acrylates, 5 parts in vinylformic acid, 0.5 part of reaction solution that forms of uncle's lauryl mercaptan, after carrying out polyreaction, neutralize with sodium hydroxide, making pH is 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, make emulsion BB (EM-BB).Get the part of this high molecular particle aqueous dispersions and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is-17 ℃.With Embodiment B-1 determining molecular weight similarly, the result is 200000.In addition, the acid number with titration measuring is 20mgKOH/g.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment B-2, use with the same method of Embodiment B-1 and obtain the jet recorded matter on fabric sample.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment B-1.The result is as shown in table 8.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment B-2, use method identical and identical evaluation method to measure ejection stability with Embodiment B-1.The measurement result of ejection stability is as shown in table 8.
(Embodiment B-3)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion B3 that use is made by following method mixes with the vehicle composition shown in the table 9, prepares ink for inkjet recording liquid.
The making of pigment dispersion B3
Pigment dispersion B3 adopts pigment violet 19 (quinacridone pigment: Clariant system), and B2 similarly makes with pigment dispersion.In addition, use the method identical with Embodiment B-1 to measure particle diameter, the result is 90nm.
(2) preparation of pigment stop bath
The emulsion BB that use is made in Embodiment B-2 mixes with the vehicle composition shown in the table 10 that contains blocked isocyanate (Xin Zhong village chemistry system NKLinkerBX), prepares the pigment stop bath.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment B-3, use the method identical to obtain the jet recorded matter on fabric sample with Embodiment B-1.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment B-1.The result is as shown in table 8.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment B-3, use method identical and identical evaluation method to measure ejection stability with Embodiment B-1.The measurement result of ejection stability is as shown in table 8.
(Embodiment B-4)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion B4 that use is made by following method mixes with the vehicle composition shown in the table 9, prepares ink for inkjet recording liquid.
The making of pigment dispersion B4
Pigment dispersion B4 adopts pigment Yellow 14 (azo pigment: Clariant system), and B2 similarly makes with pigment dispersion.Measure particle diameter with the method identical with Embodiment B-1, the result is 115nm.
(2) preparation of pigment stop bath
The emulsion BB that use is made in Embodiment B-2 mixes with the vehicle composition shown in the table 10 that contains blocked isocyanate (Xin Zhong village chemistry system NKLinkerBX), prepares the pigment stop bath.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment B-4, use the method identical to obtain the jet recorded matter on fabric sample with Embodiment B-1.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment B-1.The result is as shown in table 8.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment B-4, use method identical and identical evaluation method to measure ejection stability with Embodiment B-1.The measurement result of ejection stability is as shown in table 8.
(comparative example B-1)
In comparative example B-1, use by to operate the second-order transition temperature of making especially equally be 0 ℃ high molecular particle except the ethyl propenoate total amount in the pigment stop bath of Embodiment B-1 (45 parts) being changed into benzyl methacrylate 45, all prepare the pigment stop bath equally in addition with Embodiment B-1.The emulsion of using this high molecular particle making is as emulsion BC (EM-BC).The pigment stop bath is formed as shown in table 10.In addition, the same pigment dispersion of use and Embodiment B-1 prepares the black liquid of comparative example B-1.China ink liquid is formed as shown in table 9.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment B-1 are similarly carried out.The result is as shown in table 8.
(comparative example B-2)
In comparative example B-2, use by except all (49 parts) change benzyl methacrylate into, changing 10 parts of butyl acrylate into benzyl methacrylate 10, to operate the second-order transition temperature of making especially equally be 10 ℃ high molecular particle, all prepares the pigment stop bath equally with Embodiment B-2 in addition with the ethyl propenoate in the pigment stop bath of Embodiment B-2.The emulsion of using this high molecular particle making is as emulsion BD (EM-BD).The pigment stop bath is formed as shown in table 9.In addition, the same pigment dispersion of use and Embodiment B-2 prepares the black liquid of comparative example B-2.China ink liquid is formed as shown in table 9.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment B-1 are similarly carried out.The result is as shown in table 1.
(reference example B-3)
In reference example B-3, except the making particle diameter is the pigment dispersion of 350nm and 45nm, prepare black liquid equally with Embodiment B-3.Particle diameter adopts the method identical with Embodiment B-3 to measure.The dispersion that with particle diameter is 350nm is as pigment dispersion B3A, and the dispersion that with particle diameter is 45nm is as pigment dispersion B3B.China ink liquid is formed as shown in table 9.In addition, the pigment stop bath of reference example B-3 adopts the pigment stop bath identical with Embodiment B-3.The composition of pigment stop bath is as shown in table 10.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment B-1 are similarly carried out.The result is as shown in table 8.
(comparative example B-4)
In comparative example B-4, the acid number of the high molecular particle in the pigment stop bath that makes Embodiment B-4 is 120mgKOH/g, the 150mgKOH/g, prepares the pigment stop bath equally with Embodiment B-4.With the emulsion of using acid number to make as the high molecular particle of 120mgKOH/g as emulsion BE (EM-BE), with uses acid number as the emulsion of the high molecular particle making of 150mgKOH/g as emulsion BF (EM-BF).The pigment stop bath is formed as shown in table 10.In addition, the black liquid of comparative example B-4 adopts the black liquid identical with Embodiment B-4.China ink liquid is formed as shown in table 9.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment B-1 are similarly carried out.The result is as shown in table 8.
(comparative example B-5)
In comparative example B-5, except in the pigment stop bath of Embodiment B-2, not using the polymkeric substance (Xin Zhong village chemistry system NKLinkerFX) that contains oxazoline, similarly prepare the pigment stop bath with Embodiment B-2.The pigment stop bath is formed as shown in table 10.In addition, the black liquid of comparative example B-5 adopts the black liquid identical with Embodiment B-2.China ink liquid is formed as shown in table 9.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment B-1 are similarly carried out.The result is as shown in table 8.
(comparative example B-6)
In comparative example B-6, except in the pigment stop bath of Embodiment B-3, not using the polymkeric substance (Xin Zhong village chemistry system NKLinkerFX) that contains oxazoline, similarly prepare the pigment stop bath with Embodiment B-3.The pigment stop bath is formed as shown in table 10.In addition, the black liquid of comparative example B-6 adopts the black liquid identical with Embodiment B-3.China ink liquid is formed as shown in table 9.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment B-1 are similarly carried out.The result is as shown in table 8.
[table 8]
The result of the scuff resistance among table 8 Embodiment B-1～4, comparative example B-1～2,4～6, the reference example B-3, dry-cleaning property, ejection stability
The unit of Tg is ℃, and particle diameter is the median size of pigment, and unit is nm, and the unit of acid number is mgKOH/g.Scuff resistance, dry-cleaning property are abideed by the judgement criteria of JIS.
[table 9]
The black liquid of table 9 Embodiment B-1～4, comparative example B-1～2,4～6, reference example B-3 is formed (quality %)
The concentration of pigment is represented with solids component.
1,2-HD 1,2-hexylene glycol
1,2-PD 1,2-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 alkynol is a tensio-active agent)
The TMP TriMethylolPropane(TMP)
The TEG triglycol
The 2-P 2-Pyrrolidone
The TEA trolamine
[table 10]
The pigment stop bath of table 10 Embodiment B-1～4, comparative example B-1～2,4～6, reference example B-3 is formed (quality %)
Polymer concentration is represented with solids component.
NKLinkerFX Xin Zhong village chemistry system contains the polymer emulsion of oxazoline
1,2-HD 1,2-hexylene glycol
1,2-PD 1,2-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 alkynol 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 ink for inkjet recording liquid
The pigment dispersion B5 that use is made by following method mixes with the vehicle composition shown in the table 12, prepares ink for inkjet recording liquid.
The making of pigment dispersion B5
Pigment dispersion B5 adopts the system MA100 of Mitsubishi Chemical Industrial Co., Ltd as carbon black (PBk7).Make the carbon blacksurface oxidation and can be scattered in the water with the method identical, make dispersion B5 with Japanese patent laid-open 8-3498 communique.Measure particle diameter with the method identical with Embodiment B-1, the result is 120nm.
(2) preparation of pigment stop bath
The high molecular particle aqueous dispersions (emulsion BI) that use is made by following method mixes with the vehicle composition shown in the table 13 of the polymkeric substance that contains oxazoline (Xin Zhong village chemistry system NKLinkerFX), prepares the pigment stop bath.
The making of high molecular particle
In the reaction vessel that possesses Dropping feeder, thermometer, water-cooled reflux exchanger, stirrer, add 100 parts of ion exchanged waters, in nitrogen atmosphere gas, add 0.3 part of polymerization starter Potassium Persulphate down while stirring in 70 ℃, drip down the monomer solution that in 7 parts of ion exchanged waters, adds 0.05 part of Sodium Lauryl Sulphate BP/USP, 20 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of vinylformic acid Lauryl Ester, 5 parts of butyl methacrylate and 0.02 part of uncle's lauryl mercaptan and obtain at 70 ℃, make its reaction, make 1 time material.In this 1 material, add 2 parts of ammonium persulphate 10% solution and stirring, under 70 ℃, add while stirring then by 30 parts of ion exchanged waters, 0.2 part of lauryl potassium sulfate, 30 parts of ethyl propenoates, 25 parts of butyl acrylates, 16 parts of vinylformic acid Lauryl Ester, 5 parts in vinylformic acid, 0.5 part of reaction solution that forms of uncle's lauryl mercaptan, after carrying out polyreaction, neutralize with sodium hydroxide, making pH is 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, make emulsion BI (EM-BI).Get the part of this high molecular particle aqueous dispersions and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is-19 ℃.With the method determining molecular weight identical with Embodiment B-1, the result is 180000.In addition, the acid number with titration measuring is 18mgKOH/g.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment B-5, use with the same method of Embodiment B-1 and obtain the jet recorded matter on fabric sample.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment B-1.The result is as shown in table 11.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment B-5, use method identical and identical evaluation method to measure ejection stability with Embodiment B-1.The measurement result of ejection stability is as shown in table 11.
(Embodiment B-6)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion B6 that use is made by following method mixes with the vehicle composition shown in the table 12, prepares ink for inkjet recording liquid.
The making of pigment dispersion B6
Pigment dispersion B6 adopts pigment Blue 15: 3 (copper phthalocyanines: Clariant system).After the reaction vessel that will possess stirrer, thermometer, return line and dropping funnel carries out the nitrogen displacement, add 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 ℃, pack in dropping funnel separately 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 and Sodium Persulfates, ray flower were added drop-wise to that the limit makes dispersed polymeres carry out polyreaction in the reaction vessel in 4 hours.Then, in reaction vessel, add water, make the dispersing polymer solution of 40% concentration.Get the part of this polymkeric substance and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is 45 ℃.
With 40 parts of above-mentioned dispersing polymer solutions and 30 parts of pigment Blue 15s: 3 (copper phthalocyanines: Clariant system), 0.1mol/L aqueous sodium hydroxide solution mix for 100 parts, use the Chinese mugwort loud, high-pitched sound mill (ア イ ガ-ミ Le) that adopts the zirconium pearl to disperse 2 hours.Afterwards, transfer in other containers, add 300 parts of ion exchanged waters, stirred then 1 hour.With the sodium hydroxide neutralization of 0.1mol/L, transferring to pH is 9.Then, filter, make solids component (dispersed polymeres and pigment Blue 15: 3) be 20% dispersion B6 with the film filter of 0.3 μ m.Measure particle diameter with the method identical with Embodiment B-1, the result is 100nm.The measurement result of molecular weight is 210000.
(2) preparation of pigment stop bath
The high molecular particle aqueous dispersions (emulsion BJ) that use is made by following method mixes with the vehicle composition shown in the table 13 of the polymkeric substance that contains oxazoline (Xin Zhong village chemistry system NKLinkerFX), prepares the pigment stop bath.
The making of high molecular particle
In the reaction vessel that possesses Dropping feeder, thermometer, water-cooled reflux exchanger, stirrer, add 100 parts of ion exchanged waters, in nitrogen atmosphere gas, add 0.3 part of polymerization starter Potassium Persulphate down while stirring in 70 ℃, drip down the monomer solution that in 7 parts of ion exchanged waters, adds 0.05 part of Sodium Lauryl Sulphate BP/USP, 20 parts of ethyl propenoates, 25 parts of butyl acrylates, 6 parts of vinylformic acid Lauryl Ester, 5 parts of butyl methacrylate and 0.02 part of uncle's lauryl mercaptan and obtain at 70 ℃, make its reaction, make 1 time material.In this 1 material, add 2 parts of ammonium persulphate 10% solution and stirring, under 70 ℃, add while stirring then by 30 parts of ion exchanged waters, 0.2 part of lauryl potassium sulfate, 20 parts of ethyl propenoates, 20 parts of butyl acrylates, 20 parts of vinylformic acid Lauryl Ester, 5 parts in vinylformic acid, 0.5 part of reaction solution that forms of uncle's lauryl mercaptan, after carrying out polyreaction, neutralize with sodium hydroxide, making pH is 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, as emulsion BJ (EM-BJ).Get the part of this high molecular particle aqueous dispersions and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is-21 ℃.In addition, the acid number with titration measuring is 18mgKOH/g.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment B-6, use with the same method of Embodiment B-1 and obtain the jet recorded matter on fabric sample.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment B-1.The result is as shown in table 11.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment B-6, use method identical and identical evaluation method to measure ejection stability with Embodiment B-1.The measurement result of ejection stability is as shown in table 11.
(Embodiment B-7)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion B7 that use is made by following method mixes with the vehicle composition shown in the table 12, prepares ink for inkjet recording liquid.
The making of pigment dispersion B7
Pigment dispersion B7 adopts pigment red 122, and (dimethylquinacridone pigment: Clariant system), B6 similarly makes with pigment dispersion.Measure particle diameter with the method identical with Embodiment B-1, the result is 80nm.
(2) preparation of pigment stop bath
The emulsion BJ that use is made in Embodiment B-6 mixes with the vehicle composition shown in the table 13 of the polymkeric substance that contains oxazoline (Xin Zhong village chemistry system NKLinkerFX), prepares the pigment stop bath.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment B-7, use the method identical to obtain the jet recorded matter on fabric sample with Embodiment B-1.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment B-1.The result is as shown in table 11.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment B-7, use method identical and identical evaluation method to measure ejection stability with Embodiment B-1.The measurement result of ejection stability is as shown in table 11.
(Embodiment B-8)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion B8 that use is made by following method mixes with the vehicle composition shown in the table 12, prepares ink for inkjet recording liquid.
The making of pigment dispersion B8
Pigment dispersion B8 adopts Pigment Yellow 73 180, and (benzimidazolone is a disazo pigment: Clariant system), B6 similarly makes with pigment dispersion.Measure particle diameter with the method identical with Embodiment B-1, the result is 130nm.
(2) preparation of pigment stop bath
The emulsion BJ that use is made in Embodiment B-6 mixes with the vehicle composition shown in the table 13 of the polymkeric substance that contains oxazoline (Xin Zhong village chemistry system NKLinkerFX), prepares the pigment stop bath.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment B-8, use the method identical to obtain the jet recorded matter on fabric sample with Embodiment B-1.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment B-1.The result is as shown in table 11.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment B-8, use method identical and identical evaluation method to measure ejection stability with Embodiment B-1.The measurement result of ejection stability is as shown in table 11.
(reference example B-7)
In reference example B-7,, similarly prepare the pigment stop bath with Embodiment B-5 except the molecular weight of the high molecular particle of the pigment stop bath that makes Embodiment B-5 is 90000 and 1100000.With molecular weight be 90000 emulsion as emulsion BK (EM-BK), be that 1100000 emulsion is as emulsion BL (EM-BL) with molecular weight.The pigment stop bath is formed as shown in table 13.In addition, use the dispersible pigment dispersion identical to prepare the black liquid of reference example B-7 with Embodiment B-5.China ink liquid is formed as shown in table 12.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment B-1 are similarly carried out.The result is as shown in table 11.
(reference example B-8)
In reference example B-8, except with in the Embodiment B-6 as 1,1 of 2-aklylene glycol, the 2-hexylene glycol changes into outside the glycerine, similarly prepares black liquid and pigment stop bath with Embodiment B-6.China ink liquid is formed as shown in table 12, and the pigment stop bath is formed as shown in table 13.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment B-1 are similarly carried out.The result is as shown in table 11.
(reference example B-9)
In reference example B-9,, similarly prepare black liquid and pigment stop bath with Embodiment B-7 except being that tensio-active agent and alkynol are that tensio-active agent changes into the glycerine with the alkyne diol in the Embodiment B-7.China ink liquid is formed as shown in table 12, and the pigment stop bath is formed as shown in table 13.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment B-1 are similarly carried out.The result is as shown in table 11.
(reference example B-10)
In reference example B-10,, similarly prepare black liquid and pigment stop bath with Embodiment B-8 except the amount of the high molecular particle of the pigment stop bath in the Embodiment B-8 ratio with respect to pigment is changed into 80%, 50%.China ink liquid is formed as shown in table 12, and the pigment stop bath is formed as shown in table 13.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment B-1 are similarly carried out.The result is as shown in table 11.
(reference example B-11～15)
In reference example B-11～15, and be produced on the cotton sample that full version lettering obtains in the Embodiment B-6 equally, except carrying out similarly estimating scuff resistance with Embodiment B-6 various changes handle in 5 minutes condition of 150 ℃ of following heat treated.In order to compare with Embodiment B-6, with the example of various condition changings B-11～15 as a reference example, the result is as shown in table 14.
[table 11]
The result of the scuff resistance in table 11 Embodiment B-5～8, reference example B-7～10, dry-cleaning property, ejection stability
The unit of Tg is ℃, and particle diameter is the median size of pigment, and unit is nm, and the unit of acid number is mgKOH/g.
Molecular weight in the table 11 is * 10
5
Use % to represent to pigment ratio with respect to the high molecular particle of pigment.
Scuff resistance, dry-cleaning property are abideed by the judgement criteria of JIS.
[table 12]
The black liquid of table 12 Embodiment B-5～8 and reference example B-7～10 is formed (quality %)
Pigment concentration is represented with solids component.
1,2-HD 1,2-hexylene glycol
1,2-PD 1,2-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 alkynol is a tensio-active agent)
The TMP TriMethylolPropane(TMP)
The TEG triglycol
The 2-P 2-Pyrrolidone
The TEA trolamine
[table 13]
The pigment stop bath of table 13 Embodiment B-5～8 and reference example B-7～10 is formed (quality %)
Polymer concentration is represented with solids component.
NKLinkerFX Xin Zhong village chemistry system contains the polymer emulsion of oxazoline
1,2-HD 1,2-hexylene glycol
1,2-PD 1,2-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 alkynol is a tensio-active agent)
The TMP TriMethylolPropane(TMP)
The TEG triglycol
The 2-P 2-Pyrrolidone
The TEA trolamine
[table 14]
Frictional property test-results when changing heating condition in table 14 Embodiment B-6
(Embodiment C-1)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion C1 that use is made by following method mixes with the vehicle composition shown in the table 16, prepares ink for inkjet recording liquid.In addition, in " ion exchanged water (surplus) " in the black liquid of the present embodiment in present embodiment C and other embodiment, comparative example and reference example, contain 0.05% Mortopl Saden (ト Star プ サ イ De) 240 (the Permachem Asia corporate systems), 0.02% that are used for preventing black corrosion and be used to prevent that ink gun parts corrosive benzotriazole and 0.04% is used to reduce EDTA (ethylenediamine tetraacetic acid (EDTA)) the 2Na salt of the influence of black liquid metal ion.
The making of pigment dispersion C1
Pigment dispersion C1 adopts the system MONARCH880 of U.S. Cabot Co.,Ltd as carbon black (Pigment black 7).Make the sooty surface oxidation and can be scattered in the water with the method identical, as dispersion C1 with Japanese patent laid-open 8-3498 communique.Measure particle diameter with Microtrac particle size distribution device UPA250 (day machine dress system), the result is 110nm.
(2) preparation of pigment stop bath
The high molecular particle aqueous dispersions (emulsion CA) that use is made by following method mixes with the vehicle composition shown in the table 17 that contains poly-carbodiimide (the Carbodilite V-02 of day clear spinning), prepares the pigment stop bath.In addition, in " ion exchanged water (surplus) " in this pigment stop bath in present embodiment C and the pigment stop bath of other embodiment, comparative example and reference example, contain 0.05% Mortopl Saden (ト Star プ サ イ De) 240 (the Permachem Asia corporate systems), 0.02% that are used for preventing black corrosion and be used to prevent that ink gun parts corrosive benzotriazole and 0.04% is used to reduce EDTA (ethylenediamine tetraacetic acid (EDTA)) the 2Na salt of the influence of black liquid metal ion.
The making of high molecular particle
In the reaction vessel that possesses Dropping feeder, thermometer, water-cooled reflux exchanger, stirrer, add 100 parts of ion exchanged waters, in nitrogen atmosphere gas, add 0.2 part of polymerization starter Potassium Persulphate down while stirring in 70 ℃, drip down the monomer solution that in 7 parts of ion exchanged waters, adds 0.05 part of Sodium Lauryl Sulphate BP/USP, 4 parts of glycidoxy acrylate, 15 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of tetrahydrofurfuryl acrylates, 5 parts of butyl methacrylate and 0.02 part of uncle's lauryl mercaptan and obtain at 70 ℃, make its reaction, make 1 time material.In this 1 material, add 2 parts of ammonium persulphate 10% solution and stirring, under 70 ℃, add while stirring then by 30 parts of ion exchanged waters, 0.2 part of lauryl potassium sulfate, 30 parts of ethyl propenoates, 25 parts of methyl acrylates, 6 parts of butyl acrylates, 5 parts in vinylformic acid, 0.5 part of reaction solution that forms of uncle's lauryl mercaptan, after carrying out polyreaction, neutralize with sodium hydroxide, making pH is 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, as emulsion CA (EM-CA).Get the part of this high molecular particle aqueous dispersions and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is-15 ℃.Using the gel permeation chromatography (GPC) of system L7100 system of Hitachi Co., Ltd, is that solvent is measured with THF, and the vinylbenzene conversion molecular weight that obtains is 150000.In addition, the acid number that records with volumetry is 20mgKOH/g.
(3) manufacture method of jet recorded matter on fabric
Adopt above-mentioned black liquid, use the system PX-V600 of Seiko Epson Corp, be produced on the print that full version lettering obtains on the cotton as ink-jet printer.Then, on this print, use identical printer that above-mentioned pigment stop bath is carried out full version lettering,, obtain the jet recorded matter on fabric sample 150 ℃ of following heat treated 5 minutes.
(4) scuff resistance test and the test of dry-cleaning property
Under the 300g load, smear and state sample (jet recorded matter on fabric) 200 times with of Tai Site (テ ス -) the Industry Co., Ltd formula friction stability trier AC-301S that shakes, estimate the friction stability.According to JIS (JIS) the JIS L0849 that confirms black liquid dropping situations, estimate by dry and two moistening standards.Similarly the dry-cleaning test is estimated with the B method of JIS L0860.The result of scuff resistance test and dry-cleaning test is as shown in Table 15.
The mensuration of (5) ejection stability
Use the system PX-V600 of Seiko Epson Corp as ink-jet printer, use above-mentioned ink composition for ink-jet recording, under 35 ℃, 35% atmosphere gas, on the corporate system Xerox P of Fuji-Xerox paper A4, under Micosoft Word with No. 11 standard letters, MSP Gothic, in 100 pages of the ratio printings of 4000 word/pages or leaves and estimate.Not having the lettering entanglement fully is AA, and it is A that the lettering entanglement of 1 place is arranged, and it is B that 2 places～3 places lettering entanglement is arranged, and it is C that 4 places～5 places lettering entanglement is arranged, and it is D that the above lettering entanglement in 6 places is arranged.The result is as shown in Table 15.
(Embodiment C-2)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion C2 that use is made by following method mixes with the vehicle composition shown in the table 16, prepares ink for inkjet recording liquid.
The making of pigment dispersion C2
Pigment dispersion C2 adopts pigment Blue 15: 3 (copper phthalocyanines: Clariant system).After the reaction vessel that will possess stirrer, thermometer, return line and dropping funnel carries out the nitrogen displacement, add 75 parts of benzyl acrylates, 2 parts in vinylformic acid, 0.3 part of uncle's lauryl mercaptan, be heated to 70 ℃, pack in dropping funnel separately 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, methylethylketones preparing and Sodium Persulfate, ray flower were added drop-wise to that the limit makes dispersed polymeres carry out polyreaction in the reaction vessel in 4 hours.Then, in reaction vessel, add methylethylketone, make the dispersing polymer solution of 40% concentration.Get the part of this polymkeric substance and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is 40 ℃.
With 40 parts of above-mentioned dispersing polymer solutions and 30 parts of pigment Blue 15s: 3,100 parts of 0.1mol/L aqueous sodium hydroxide solutions, methylethylketone mix for 30 parts.Use ultra-high voltage homogenizer (the wild machinery system of Co., Ltd. China fir Altimizer HJP-25005) under 200MPa, to disperse then by (pass) 15.Afterwards, transfer in other containers, add 300 parts of ion exchanged waters, stirred then 1 hour.Heat up in a steamer whole methylethylketones and a part of water with rotatory evaporator, the sodium hydroxide neutralization with 0.1mol/L transfers to pH 9.Then, filter, regulate, obtain pigment concentration and be 15% pigment dispersion C2 with ion exchanged water with the film filter of 0.3 μ m.Measure particle diameter with the method identical with Embodiment C-1, the result is 80nm.
(2) preparation of pigment stop bath
The high molecular particle aqueous dispersions (emulsion CB) that use is made by following method mixes with the vehicle composition shown in the table 17 that contains poly-carbodiimide (day clear spinning Carbodilite V-02), prepares the pigment stop bath.
The making of high molecular particle
In the reaction vessel that possesses Dropping feeder, thermometer, water-cooled reflux exchanger, stirrer, add 100 parts of ion exchanged waters, in nitrogen atmosphere gas, add 0.2 part of polymerization starter Potassium Persulphate down while stirring in 70 ℃, drip down the monomer solution that in 7 parts of ion exchanged waters, adds 0.05 part of Sodium Lauryl Sulphate BP/USP, 19 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of tetrahydrofurfuryl acrylates, 5 parts of butyl methacrylate and 0.02 part of uncle's lauryl mercaptan and obtain at 70 ℃, make its reaction, make 1 time material.In this 1 material, add 2 parts of ammonium persulphate 10% solution and stirring, under 70 ℃, add while stirring then by 30 parts of ion exchanged waters, 0.2 part of lauryl potassium sulfate, 30 parts of ethyl propenoates, 25 parts of methyl acrylates, 16 parts of butyl acrylates, 5 parts in vinylformic acid, 0.5 part of reaction solution that forms of uncle's lauryl mercaptan, after carrying out polyreaction, neutralize with sodium hydroxide, making pH is 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, as emulsion CB (EM-CB).Get the part of this high molecular particle aqueous dispersions and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is-17 ℃.With Embodiment C-1 determining molecular weight similarly, the result is 200000.In addition, the acid number with titration measuring is 20mgKOH/g.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment C-2, use with the same method of Embodiment C-1 and obtain the jet recorded matter on fabric sample.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment C-1.The result is as shown in Table 15.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment C-2, use method identical and identical evaluation method to measure ejection stability with Embodiment C-1.The measurement result of ejection stability is as shown in Table 15.
(Embodiment C-3)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion C3 that use is made by following method mixes with the vehicle composition shown in the table 16, prepares ink for inkjet recording liquid.
The making of pigment dispersion C3
Pigment dispersion C3 adopts pigment violet 19 (quinacridone pigment: Clariant system), and C2 similarly makes with pigment dispersion.In addition, use the method identical with Embodiment C-1 to measure particle diameter, the result is 90nm.
(2) preparation of pigment stop bath
The emulsion CB that use is made in Embodiment C-2 mixes with the vehicle composition shown in the table 17 that contains poly-carbodiimide (day clear spinning Carbodilite V-02), prepares the pigment stop bath.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment C-3, use the method identical to obtain the jet recorded matter on fabric sample with Embodiment C-1.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment C-1.The result is as shown in Table 15.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment C-3, use method identical and identical evaluation method to measure ejection stability with Embodiment C-1.The measurement result of ejection stability is as shown in Table 15.
(Embodiment C-4)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion C4 that use is made by following method mixes with the vehicle composition shown in the table 16, prepares ink for inkjet recording liquid.
The making of pigment dispersion C4
Pigment dispersion C4 adopts pigment Yellow 14 (azo pigment: Clariant system), and C2 similarly makes with pigment dispersion.Measure particle diameter with the method identical with Embodiment C-1, the result is 115nm.
(2) preparation of pigment stop bath
The emulsion CB that use is made in Embodiment C-2 mixes with the vehicle composition shown in the table 17 that contains poly-carbodiimide (day clear spinning Carbodilite V-02), prepares the pigment stop bath.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment C-4, use the method identical to obtain the jet recorded matter on fabric sample with Embodiment C-1.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment C-1.The result is as shown in Table 15.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment C-4, use method identical and identical evaluation method to measure ejection stability with Embodiment C-1.The measurement result of ejection stability is as shown in Table 15.
(comparative example C-1)
In comparative example C-1, use by to operate the second-order transition temperature of making especially equally be 0 ℃ high molecular particle except the ethyl propenoate total amount in the pigment stop bath of Embodiment C-1 (45 parts) being changed into benzyl methacrylate 45, all prepare the pigment stop bath equally in addition with Embodiment C-1.The emulsion of using this high molecular particle making is as emulsion CC (EM-CC).The pigment stop bath is formed shown in table 17.In addition, the same dispersible pigment dispersion of use and Embodiment C-1 prepares the black liquid of comparative example C-1.China ink liquid is formed shown in table 16.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment C-1 are similarly carried out.The result is as shown in Table 15.
(comparative example C-2)
In comparative example C-2, use by except the ethyl propenoate total amount in the pigment stop bath of Embodiment C-2 (49 parts) is changed into benzyl methacrylate, changing 10 parts of butyl acrylate into benzyl methacrylate 10, to operate the second-order transition temperature of making especially equally be 10 ℃ high molecular particle, all prepares the pigment stop bath equally with Embodiment C-2 in addition.The emulsion of using this high molecular particle making is as emulsion CD (EM-CD).The pigment stop bath is formed shown in table 17.In addition, the same dispersible pigment dispersion of use and Embodiment C-2 prepares the black liquid of comparative example C-2.China ink liquid is formed shown in table 16.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment C-1 are similarly carried out.The result is as shown in Table 15.
(reference example C-3)
In reference example C-3, except the making particle diameter is the pigment dispersion of 350nm and 45nm, prepare black liquid equally with Embodiment C-3.Particle diameter adopts the method identical with Embodiment C-3 to measure.The dispersion that with particle diameter is 350nm is as pigment dispersion C3A, and the dispersion that with particle diameter is 45nm is as pigment dispersion C3B.China ink liquid is formed shown in table 16.In addition, the pigment stop bath of reference example C-3 adopts the pigment stop bath identical with Embodiment C-3.The pigment stop bath is formed shown in table 17.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment C-1 are similarly carried out.The result is as shown in Table 15.
(comparative example C-4)
In comparative example C-4, the acid number of the high molecular particle in the pigment stop bath that makes Embodiment C-4 is 120mgKOH/g, the 150mgKOH/g, prepares the pigment stop bath equally with Embodiment C-4.With the emulsion of using acid number to make as the high molecular particle of 120mgKOH/g as emulsion CE (EM-CE), with uses acid number as the emulsion of the high molecular particle making of 150mgKOH/g as emulsion CF (EM-CF).The pigment stop bath is formed shown in table 17.In addition, the black liquid of comparative example C-4 adopts the black liquid identical with Embodiment C-4.China ink liquid is formed shown in table 16.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment C-1 are similarly carried out.The result is as shown in Table 15.
(comparative example C-5)
In comparative example C-5, except in the pigment stop bath of Embodiment C-2, not using poly-carbodiimide (day clear spinning Carbodilite V-02), similarly prepare the pigment stop bath with Embodiment C-2.The pigment stop bath is formed shown in table 17.In addition, the black liquid of comparative example C-5 adopts the black liquid identical with Embodiment C-2.China ink liquid is formed shown in table 16.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment C-1 are similarly carried out.The result is as shown in Table 15.
(comparative example C-6)
In comparative example C-6, except in the pigment stop bath of Embodiment C-3, not using poly-carbodiimide (day clear spinning Carbodilite V-02), similarly prepare the pigment stop bath with Embodiment C-3.The pigment stop bath is formed shown in table 17.In addition, the black liquid of comparative example C-6 adopts the black liquid identical with Embodiment C-3.China ink liquid is formed shown in table 16.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment C-1 are similarly carried out.The result is as shown in Table 15.
[table 15]
The result of the scuff resistance among table 15 Embodiment C-1～4, comparative example C-1～2,4～6, the reference example C-3, dry-cleaning property, ejection stability
The unit of Tg is ℃, and particle diameter is the median size of pigment, and unit is nm, and the unit of acid number is mgKOH/g.Scuff resistance, dry-cleaning property are abideed by the judgement criteria of JIS.
[table 16]
The black liquid of table 16 Embodiment C-1～4, comparative example C-1～2,4～6, reference example C-3 is formed (quality %)
The concentration of pigment is represented with solids component.
1,2-HD 1,2-hexylene glycol
1,2-PD 1,2-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 alkynol is a tensio-active agent)
The TMP TriMethylolPropane(TMP)
The TEG triglycol
The 2-P 2-Pyrrolidone
The TEA trolamine
[table 17]
The pigment stop bath of table 17 Embodiment C-1～4, comparative example C-1～2,4～6, reference example C-3 is formed (quality %)
Polymer concentration is represented with solids component.
V-02 gathers carbodiimide (day clear spinning Carbodilite V-02)
1,2-HD 1,2-hexylene glycol
1,2-PD 1,2-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 alkynol is a tensio-active agent)
The TMP TriMethylolPropane(TMP)
The TEG triglycol
The 2-P 2-Pyrrolidone
The TEA trolamine
(Embodiment C-5)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion C5 that use is made by following method mixes with the vehicle composition shown in the table 19, prepares ink for inkjet recording liquid.
The making of pigment dispersion C5
Pigment dispersion C5 adopts the system MA100 of Mitsubishi Chemical Industrial Co., Ltd as carbon black (PBk7).Make the carbon blacksurface oxidation and can be scattered in the water with the method identical, as dispersion C5 with Japanese patent laid-open 8-3498 communique.Measure particle diameter with the method identical with Embodiment C-1, the result is 120nm.
(2) preparation of pigment stop bath
The high molecular particle aqueous dispersions (emulsion CI) that use is made by following method mixes with the vehicle composition shown in the table 20 that contains poly-carbodiimide (day clear spinning Carbodilite V-02), prepares the pigment stop bath.
The making of high molecular particle
In the reaction vessel that possesses Dropping feeder, thermometer, water-cooled reflux exchanger, stirrer, add 100 parts of ion exchanged waters, in nitrogen atmosphere gas, add 0.3 part of polymerization starter Potassium Persulphate down while stirring in 70 ℃, drip down the monomer solution that in 7 parts of ion exchanged waters, adds 0.05 part of Sodium Lauryl Sulphate BP/USP, 20 parts of ethyl propenoates, 15 parts of butyl acrylates, 6 parts of vinylformic acid Lauryl Ester, 5 parts of butyl methacrylate and 0.02 part of uncle's lauryl mercaptan and obtain at 70 ℃, make its reaction, make 1 time material.In this 1 material, add 2 parts of ammonium persulphate 10% solution and stirring, under 70 ℃, add while stirring then by 30 parts of ion exchanged waters, 0.2 part of lauryl potassium sulfate, 30 parts of ethyl propenoates, 25 parts of butyl acrylates, 16 parts of vinylformic acid Lauryl Ester, 5 parts in vinylformic acid, 0.5 part of reaction solution that forms of uncle's lauryl mercaptan, after carrying out polyreaction, neutralize with sodium hydroxide, making pH is 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, make emulsion CI (EM-CI).Get the part of this high molecular particle aqueous dispersions and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is-19 ℃.With the method determining molecular weight identical with Embodiment C-1, the result is 180000.In addition, the acid number with titration measuring is 18mgKOH/g.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment C-5, use with the same method of Embodiment C-1 and obtain the jet recorded matter on fabric sample.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment C-1.The result is shown in table 18.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment C-5, use method identical and identical evaluation method to measure ejection stability with Embodiment C-1.The measurement result of ejection stability is shown in table 18.
(Embodiment C-6)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion C6 that use is made by following method mixes with the vehicle composition shown in the table 19, prepares ink for inkjet recording liquid.
The making of pigment dispersion C6
Pigment dispersion C6 adopts pigment Blue 15: 3 (copper phthalocyanines: Clariant system).After the reaction vessel that will possess stirrer, thermometer, return line and dropping funnel carries out the nitrogen displacement, add 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 ℃, pack in dropping funnel separately 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 and Sodium Persulfates, ray flower were added drop-wise to that the limit makes dispersed polymeres carry out polyreaction in the reaction vessel in 4 hours.Then, in reaction vessel, add water, make the dispersing polymer solution of 40% concentration.Get the part of this polymkeric substance and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is 45 ℃.
With 40 parts of above-mentioned dispersing polymer solutions and 30 parts of pigment Blue 15s: 3 (copper phthalocyanines: Clariant system), 0.1mol/L aqueous sodium hydroxide solution mix for 100 parts, use the Chinese mugwort loud, high-pitched sound mill (ア イ ガ-ミ Le) that adopts the zirconium pearl to disperse 2 hours.Afterwards, transfer in other containers, add 300 parts of ion exchanged waters, stirred then 1 hour.Sodium hydroxide neutralization with 0.1mol/L transfers to pH 9.Then, filter, make solids component (dispersed polymeres and pigment Blue 15: 3) be 20% dispersion C6 with the film filter of 0.3 μ m.Measure particle diameter with the method identical with Embodiment C-1, the result is 100nm.The measurement result of molecular weight is 210000.
(2) preparation of pigment stop bath
The high molecular particle aqueous dispersions (emulsion CJ) that use is made by following method mixes with the vehicle composition shown in the table 20 that contains poly-carbodiimide (day clear spinning Carbodilite V-02), prepares the pigment stop bath.
The making of high molecular particle
In the reaction vessel that possesses Dropping feeder, thermometer, water-cooled reflux exchanger, stirrer, add 100 parts of ion exchanged waters, in nitrogen atmosphere gas, add 0.3 part of polymerization starter Potassium Persulphate down while stirring in 70 ℃, drip down the monomer solution that in 7 parts of ion exchanged waters, adds 0.05 part of Sodium Lauryl Sulphate BP/USP, 20 parts of ethyl propenoates, 25 parts of butyl acrylates, 6 parts of vinylformic acid Lauryl Ester, 5 parts of butyl methacrylate and 0.02 part of uncle's lauryl mercaptan and obtain at 70 ℃, make its reaction, make 1 time material.In this 1 material, add 2 parts of ammonium persulphate 10% solution and stirring, under 70 ℃, add while stirring then by 30 parts of ion exchanged waters, 0.2 part of lauryl potassium sulfate, 20 parts of ethyl propenoates, 20 parts of butyl acrylates, 20 parts of vinylformic acid Lauryl Ester, 5 parts in vinylformic acid, 0.5 part of reaction solution that forms of uncle's lauryl mercaptan, after carrying out polyreaction, neutralize with sodium hydroxide, making pH is 8～8.5, strainer with 0.3 μ m filters, make the high molecular particle aqueous dispersions, as emulsion CJ (EM-CJ).Get the part of this high molecular particle aqueous dispersions and make its drying, use differential scanning type calorimeter (Seiko electronics system EXSTAR6000DSC) to measure second-order transition temperature then, the result is-21 ℃.In addition, the acid number with titration measuring is 18mgKOH/g.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment C-6, use with the same method of Embodiment C-1 and obtain the jet recorded matter on fabric sample.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment C-1.The result is shown in table 18.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment C-6, use method identical and identical evaluation method to measure ejection stability with Embodiment C-1.The measurement result of ejection stability is shown in table 18.
(Embodiment C-7)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion C7 that use is made by following method mixes with the vehicle composition shown in the table 19, prepares ink for inkjet recording liquid.
The making of pigment dispersion C7
Pigment dispersion C7 adopts pigment red 122, and (dimethylquinacridone pigment: Clariant system), C6 similarly makes with pigment dispersion.Measure particle diameter with the method identical with Embodiment C-1, the result is 80nm.
(2) preparation of pigment stop bath
The emulsion CJ that use is made in Embodiment C-6 mixes with the vehicle composition shown in the table 20 that contains poly-carbodiimide (day clear spinning Carbodilite V-02), prepares the pigment stop bath.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment C-7, use the method identical to obtain the jet recorded matter on fabric sample with Embodiment C-1.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment C-1.The result is shown in table 18.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment C-7, use method identical and identical evaluation method to measure ejection stability with Embodiment C-1.The measurement result of ejection stability is shown in table 18.
(Embodiment C-8)
(1) preparation of ink for inkjet recording liquid
The pigment dispersion C8 that use is made by following method mixes with the vehicle composition shown in the table 19, prepares ink for inkjet recording liquid.
The making of pigment dispersion C8
Pigment dispersion C8 adopts Pigment Yellow 73 180, and (benzimidazolone is a disazo pigment: Clariant system), C6 similarly makes with pigment dispersion.Measure particle diameter with the method identical with Embodiment C-1, the result is 130nm.
(2) preparation of pigment stop bath
The emulsion CJ that use is made in Embodiment C-6 mixes with the vehicle composition shown in the table 20 that contains poly-carbodiimide (day clear spinning Carbodilite V-02), prepares the pigment stop bath.
(3) manufacture method of jet recorded matter on fabric
Use the black liquid and the pigment stop bath of Embodiment C-8, use the method identical to obtain the jet recorded matter on fabric sample with Embodiment C-1.
(4) scuff resistance test and the test of dry-cleaning property
To above-mentioned sample (jet recorded matter on fabric), similarly carry out scuff resistance test and the test of dry-cleaning property with Embodiment C-1.The result is shown in table 18.
The mensuration of (5) ejection stability
Use the black liquid of Embodiment C-8, use method identical and identical evaluation method to measure ejection stability with Embodiment C-1.The measurement result of ejection stability is shown in table 18.
(reference example C-7)
In reference example C-7,, similarly prepare the pigment stop bath with Embodiment C-5 except the molecular weight of the high molecular particle of the pigment stop bath that makes Embodiment C-5 is 90000 and 1100000.With molecular weight be 90000 emulsion as emulsion CK (EM-CK), be that 1100000 emulsion is as emulsion CL (EM-CL) with molecular weight.The pigment stop bath is formed shown in table 20.In addition, use the dispersible pigment dispersion identical to prepare the black liquid of reference example C-7 with Embodiment C-5.China ink liquid is formed shown in table 19.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment C-1 are similarly carried out.The result is shown in table 18.
(reference example C-8)
In reference example C-8, except with in the Embodiment C-6 as 1,1 of 2-aklylene glycol, the 2-hexylene glycol changes into outside the glycerine, similarly prepares black liquid and pigment stop bath with Embodiment C-6.China ink liquid is formed shown in table 19, and the pigment stop bath is formed shown in table 20.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment C-1 are similarly carried out.The result is shown in table 18.
(reference example C-9)
In reference example C-9,, similarly prepare black liquid and pigment stop bath with Embodiment C-7 except being that tensio-active agent and alkynol are that tensio-active agent changes into the glycerine with the alkyne diol in the Embodiment C-7.China ink liquid is formed shown in table 19, and the pigment stop bath is formed shown in table 20.The preparation of jet recorded matter on fabric sample, scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment C-1 are similarly carried out.The result is shown in table 18.
(reference example C-10)
In reference example C-10,, similarly prepare black liquid and pigment stop bath with Embodiment C-8 except the amount of the high molecular particle of the pigment stop bath in the Embodiment C-8 ratio with respect to pigment is changed into 80%, 50%.The pigment stop bath is formed shown in table 20, and ink composition is shown in table 19.Scuff resistance test, the test of dry-cleaning property and ejection stability test and Embodiment C-1 are similarly carried out.The result is shown in table 18.
(reference example C-11～15)
In reference example C-11～15, and be produced on the cotton sample that full version lettering obtains in the Embodiment C-6 equally, except carrying out similarly estimating scuff resistance with Embodiment C-6 various changes handle in 5 minutes condition of 150 ℃ of following heat treated.In order to compare with Embodiment C-6, with the example of various condition changings C-11～15 as a reference example, the result is shown in table 21.
[table 18]
The result of the scuff resistance in table 18 Embodiment C-5～8, reference example C-7～10, dry-cleaning property, ejection stability
The unit of Tg is ℃, and particle diameter is the median size of pigment, and unit is nm, and the unit of acid number is mgKOH/g.
Molecular weight in the table 18 is * 10
5
Use % to represent to pigment ratio with respect to the high molecular particle of pigment.
Scuff resistance, dry-cleaning property are abideed by the judgement criteria of JIS.
[table 19]
The black liquid of table 19 Embodiment C-5～8 and reference example C-7～10 is formed (quality %)
Pigment concentration is represented with solids component.
1,2-HD 1,2-hexylene glycol
1,2-PD 1,2-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 alkynol is a tensio-active agent)
The TMP TriMethylolPropane(TMP)
The TEG triglycol
The 2-P 2-Pyrrolidone
The TEA trolamine
[table 20]
The pigment stop bath of table 20 Embodiment C-5～8 and reference example C-7～10 is formed (quality %)
Polymer concentration is represented with solids component.
V-02 gathers carbodiimide (day clear spinning Carbodilite V-02)
1,2-HD 1,2-hexylene glycol
1,2-PD 1,2-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 alkynol is a tensio-active agent)
The TMP TriMethylolPropane(TMP)
The TEG triglycol
The 2-P 2-Pyrrolidone
The TEA trolamine
[table 21]
Frictional property test-results when changing heating condition in table 21 Embodiment C-6
Claims (21)
1. a pigment stop bath is characterized in that,
Contain high molecular particle and reagent,
The second-order transition temperature of described high molecular particle below-10 ℃, acid number below 100mgKOH/g, and use (methyl) alkyl acrylate and/or (methyl) vinylformic acid cyclic alkyl ester to synthesize at least as its constituent.
2. pigment stop bath according to claim 1 is characterized in that,
Described reagent is at least a kind that selects from the group that polymkeric substance and poly-carbodiimide by blocked isocyanate, Han oxazoline constitute.
3. pigment stop bath according to claim 1 and 2 is characterized in that,
It is described (methyl) alkyl acrylate and/or (methyl) vinylformic acid cyclic alkyl ester more than the 70 quality % that described pigment stop bath contains with respect to described high molecular particle total amount.
4. according to each described pigment stop bath in the claim 1～3, it is characterized in that,
Described (methyl) alkyl acrylate and/or (methyl) vinylformic acid cyclic alkyl ester are (methyl) vinylformic acid C
1～C
24Alkyl ester and/or (methyl) vinylformic acid ring-type C
3～C
24Alkyl ester.
5. according to each described pigment stop bath in the claim 1～4, it is characterized in that,
The vinylbenzene conversion weight-average molecular weight that described high molecular particle is recorded by gel permeation chromatography (GPC) is more than 100000 below 1000000.
6. a black liquid group is characterized in that,
Have each described pigment stop bath in ink composition and the claim 1～5,
Described ink composition contains can be with the dispersion of colo(u)rant dispersion in water.
7. black liquid group according to claim 6 is characterized in that,
The median size of described dispersion is below the above 300nm of 50nm.
8. black liquid group according to claim 7 is characterized in that,
Described dispersion for do not use dispersion agent just can be scattered in the water median size as below the above 300nm of 50nm from disperse black carbon.
9. black liquid group according to claim 7 is characterized in that,
Described dispersion be for can use polymkeric substance that the median size that pigment dyestuff is scattered 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.
10. according to each described black liquid group in the claim 6～9, it is characterized in that,
Described ink composition contains 1, the 2-aklylene glycol.
11. according to each described black liquid group in the claim 6～10, it is characterized in that,
It is that tensio-active agent and/or alkynol are tensio-active agent that described ink composition contains alkyne diol.
12. according to each described black liquid group in the claim 6～11, it is characterized in that,
The content of described high molecular particle (quality %) is more than the content (quality %) of described pigment.
13. the manufacture method of a jet recorded matter on fabric is characterized in that, has:
To contain the ink composition of following dispersion carries out ink jet printing on cloth operation, described dispersion is can be with the dispersion of colo(u)rant dispersion in water;
This print be impregnated in the operation in each described pigment stop bath in the claim 1～5; With
With this dipping after print in the operation of thermal treatment below 200 ℃ more than 1 minute more than 110 ℃.
14. the manufacture method of a jet recorded matter on fabric is characterized in that, has:
To contain the ink composition of following dispersion carries out ink jet printing on cloth operation, described dispersion is can be with the dispersion of colo(u)rant dispersion in water;
Utilize ink jet method each described pigment stop bath in the claim 1～5 to be coated the operation of this print; With
With this coating after print in the operation of thermal treatment below 200 ℃ more than 1 minute more than 110 ℃.
15. the manufacture method according to claim 13 or 14 described jet recorded matter on fabric is characterized in that,
The median size of described dispersion is below the above 300nm of 50nm.
16. the manufacture method of jet recorded matter on fabric according to claim 15 is characterized in that,
Described dispersion for do not use dispersion agent just can be scattered in the water median size as below the above 300nm of 50nm from disperse black carbon.
17. the manufacture method of jet recorded matter on fabric according to claim 15 is characterized in that,
Described dispersion be for can use polymkeric substance that the median size that pigment dyestuff is scattered 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.
18. the manufacture method according to each described jet recorded matter on fabric in the claim 13～17 is characterized in that,
Described ink composition contains 1, the 2-aklylene glycol.
19. the manufacture method according to each described jet recorded matter on fabric in the claim 13～18 is characterized in that,
It is that tensio-active agent and/or alkynol are tensio-active agent that described ink composition contains alkyne diol.
20. the manufacture method according to each described jet recorded matter on fabric in the claim 13～19 is characterized in that,
The content of described high molecular particle (quality %) is more than the content (quality %) of described pigment.
21. a jet recorded matter on fabric is characterized in that,
Manufacture method by each described jet recorded matter on fabric in the claim 13～20 obtains.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008055901 | 2008-03-06 | ||
| JP2008055901 | 2008-03-06 | ||
| JP2008055903 | 2008-03-06 | ||
| JP2008310594 | 2008-12-05 | ||
| JP2009030343 | 2009-02-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101525463A true CN101525463A (en) | 2009-09-09 |
Family
ID=41093541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009101265013A Pending CN101525463A (en) | 2008-03-06 | 2009-03-06 | Liquid composition for making pigment fixed, ink set, method for producing ink jet recorded matter on fabric and ink jet recorded matter on fabric |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101525463A (en) |
-
2009
- 2009-03-06 CN CNA2009101265013A patent/CN101525463A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101880494B (en) | Ink composition for ink jet recording | |
| CN105040441B (en) | Ink jet printing method | |
| JP2010156089A (en) | Pigment fixing solution, ink set, method for producing printed matter and resultant printed matter | |
| CN101861367B (en) | Ink composition | |
| KR102210018B1 (en) | Aqueous ink-jet inks containing two or more binders | |
| JP2010155959A (en) | Ink set, method for producing printed matter, and printed matter | |
| JP2010077381A (en) | Ink composition, inkjet-printing ink, inkjet printing method, method for producing inkjet printed matter, and the resultant inkjet printed matter | |
| JP2010155444A (en) | Ink set, method of manufacturing printed matter, and printed matter | |
| JP2009235386A (en) | Ink composition, inkjet recording ink, inkjet recording method, manufacturing method for inkjet printed matter, and inkjet printed matter | |
| JP2010043149A (en) | Ink set | |
| CN101205431A (en) | Ink-jet recording ink | |
| US20090233063A1 (en) | Liquid composition for making pigment fixed, ink set, method for producing ink jet recorded matter on fabric and ink jet recorded matter on fabric | |
| CN101205430B (en) | Ink-jet recording ink | |
| US20230265303A1 (en) | White inkjet ink | |
| CN101525513A (en) | Ink composition, ink composition for ink jet recording, ink jet recording method, method for producing ink jet recorded matter and ink jet recorded matter | |
| JP5625275B2 (en) | Inkjet recording method | |
| JP2013071957A (en) | Ink set for inkjet printing and printing method | |
| CN101531847A (en) | Ink set, method for producing ink jet recorded matter on fabric and ink jet recorded matter on fabric | |
| CN101525463A (en) | Liquid composition for making pigment fixed, ink set, method for producing ink jet recorded matter on fabric and ink jet recorded matter on fabric | |
| US10196531B2 (en) | Pigmented inkjet ink comprising dispersed polyurethane and olefin ionic copolymer | |
| CN101525512A (en) | Ink composition, ink composition for ink jet recording, ink jet recording method, method for producing ink jet recorded matter and ink jet recorded matter | |
| WO2017079288A1 (en) | Aqueous ink-jet ink containing low boiling point solvents | |
| CN101531846A (en) | Ink set, method for producing ink jet recorded matter on fabric and ink jet recorded matter on fabric | |
| CN101525462A (en) | Liquid composition for making pigment fixed, ink set, method for producing ink jet recorded matter on fabric and ink jet recorded matter on fabric | |
| EP3030619A2 (en) | Aqueous inkjet inks containing polymeric binders with components to interact with cellulose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20090909 |
|
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |