阅读说明：本技术 油墨用分散液组合物及油墨组合物 (Dispersion composition for ink and ink composition ) 是由 佐佐木桂丈 宫泽由昌 花里秋津 樋口比吕子 于 2020-02-17 设计创作，主要内容包括：本发明提供含有水不溶性着色剂、水溶性多糖类化合物、多价金属盐、分散剂及水的油墨用分散液组合物、以及含有该油墨用分散液组合物的油墨组合物。另外,提供使用了该油墨组合物的喷墨印刷方法及利用该喷墨印刷方法进行印刷而得到的喷墨印刷物、以及使用了该喷墨印刷物的升华转印染色方法及利用该升华转印染色方法进行染色而得到的升华转印染色物。(The invention provides a dispersion liquid composition for ink containing a water-insoluble colorant, a water-soluble polysaccharide compound, a polyvalent metal salt, a dispersant and water, and an ink composition containing the dispersion liquid composition for ink. Also provided are an inkjet printing method using the ink composition, an inkjet printed matter obtained by printing using the inkjet printing method, a sublimation transfer dyeing method using the inkjet printed matter, and a sublimation transfer dyed matter obtained by dyeing using the sublimation transfer dyeing method.)

1. A dispersion composition for ink, which contains a water-insoluble coloring agent, a water-soluble polysaccharide compound, a polyvalent metal salt, a dispersant and water.

2. The dispersion composition for ink according to claim 1, wherein the water-insoluble colorant comprises at least one selected from the group consisting of a disperse dye and an oil-soluble dye.

3. The dispersion composition for ink according to claim 1 or2, wherein the water-soluble polysaccharide compound contains at least one selected from the group consisting of alginic acid compounds, pectin compounds, carrageenan compounds, carboxymethyl cellulose compounds, and agar.

4. The dispersion composition for ink according to any one of claims 1 to 3, wherein the polyvalent metal salt comprises a salt of at least one metal selected from the group consisting of Ca, Mg, Ti, Al, Zn, Fe, Co, Ni, and Cu.

5. The dispersion composition for ink according to any one of claims 1 to 4, wherein the dispersant comprises at least one selected from the group consisting of an anionic dispersant, a nonionic dispersant, and a polymeric dispersant.

6. The dispersion composition for ink according to claim 5, wherein the anionic dispersant comprises at least one selected from the group consisting of a formalin condensate of β -naphthalenesulfonate, a formalin condensate of alkylnaphthalenesulfonate, and a formalin condensate of creosol sulfonate.

7. The dispersion composition for ink according to claim 5 or6, wherein the nonionic dispersant comprises at least one selected from the group consisting of an ethylene oxide adduct of a phytosterol and an ethylene oxide adduct of a cholestane alcohol.

8. The dispersion composition for ink according to any one of claims 5 to 7, wherein the polymer dispersant comprises a styrene- (meth) acrylic acid copolymer.

9. The dispersion composition for ink according to any one of claims 1 to 8, further comprising an antifoaming agent.

10. The dispersion composition for ink according to any one of claims 1 to 9, further comprising a water-soluble organic solvent.

11. The dispersion composition for ink according to any one of claims 1 to 10, further comprising a preservative.

12. The dispersion composition for ink according to any one of claims 1 to 11, which comprises particles comprising the water-insoluble colorant, the water-soluble polysaccharide compound, and the polyvalent metal salt, and which have a number average particle diameter of 10 to 500 nm.

13. An ink composition comprising the dispersion composition for ink according to any one of claims 1 to 12.

14. An ink jet printing method, wherein the ink composition according to claim 13 is used as an ink, and droplets of the ink are attached to a recording medium by an ink jet printer to perform printing.

15. An inkjet printed material obtained by printing by the inkjet printing method according to claim 14.

16. A sublimation transfer dyeing method, wherein the inkjet printed material according to claim 15 is heated, and a water-insoluble colorant applied to the inkjet printed material is sublimation transferred to a target object to be dyed.

17. A sublimation transfer-printed material dyed by the sublimation transfer-printing dyeing method according to claim 16.

Technical Field

The present invention relates to a dispersion composition for ink and an ink composition.

Background

With the progress of information digitization, inkjet printers have become widely popular as printers for office and home use. In recent years, the development of applications to commercial printing, textile printing, and the like has been greatly advanced. Further, as the use of ink jet printers has become widespread, various colorants such as water-soluble colorants such as acid dyes and direct dyes, and water-insoluble colorants such as disperse dyes and pigments have come to be used as colorants for inks depending on the use.

Disperse dyes are widely used for industrial dyeing of hydrophobic fibers such as polyester, and are used for dyeing by dispersing in a dye bath or in a color paste. The dye permeates and diffuses into the fiber in a dispersed state under high temperature conditions, and is colored by fiber-dye hydrogen bonds, intermolecular forces, and the like. If the dispersibility of the dye, particularly at high temperatures, is poor, the dye aggregates in the high-temperature dye bath, and spots are likely to occur on the fibers. Therefore, conventionally, dispersants having excellent high-temperature dispersibility, for example, anionic dispersants such as formaldehyde condensates of lignosulfonic acid, formaldehyde condensates of alkylnaphthalenesulfonic acid, and formaldehyde condensates of creosol sulfonic acid have been mainly used for fiber dyeing.

Inkjet printing of polyester fibers using a disperse dye has also been carried out, and the following printing methods have been put into practical use: a direct printing method in which a dye ink is applied (printed) to a fiber and then the fiber is colored by heat treatment such as steaming; and a thermal transfer printing method in which after a dye ink is applied (printed) to an intermediate recording medium (special transfer paper), the dye is sublimation-transferred from the intermediate recording medium side to the fiber side by heat. In the dispersion of dye inks used for these printing, anionic dispersants used for industrial dyeing have been used (see patent documents 1 and 2). However, according to the studies of the inventors of the present application, it has been found that these anionic dispersants have a problem in sedimentation stability in a dispersion liquid and also have a problem in ejection stability of an ink formed into an ink. Further, it is known that the use of the dispersant represented by formula 1 in patent document 3 has a problem in sedimentation stability (storage stability) although ejection stability is good.

In order to expand the field of use of printing methods using inks in the future, inks used in inkjet printing and colored bodies colored with the inks are required to exhibit high color development and to have excellent various fastness properties such as light fastness and water resistance. Further, inks used in inkjet printing are strongly required to have excellent storage stability and to be re-dissolved or dispersed in water after drying. Particularly, an ink using a disperse dye is required to have excellent storage stability. It is known that a dye which is generally present in an ink as particles (not molecules) in a dispersed state undergoes a sedimentation phenomenon over time due to aggregation of dye particles. Therefore, if the storage stability of the ink is poor, there is a problem that: a concentration gradient is generated in the ink, and desired printing characteristics cannot be obtained; or, in the worst case, the aggregated particles clog the nozzle and become a state in which ejection is impossible. There is a demand for development of various inks excellent in fastness, high in density of printed images, and good in storage stability, but at present, there are few inks having sufficient performance.

Examples of the ink using a pigment include the ink of patent document 6. This is an ink obtained by preparing a dispersion using a polymer dispersant. Further, patent document 5 discloses an ink using a self-dispersible pigment. In recent years, microcapsule pigments using self-assembled pigments have been widely studied and studied as means for solving the above problems, and patent document 8 discloses a production method thereof. However, all inks have not yet fully met the market requirements.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 9-291235

Patent document 2: japanese laid-open patent publication No. 8-333531

Patent document 3: japanese patent laid-open publication No. 2003-246954

Patent document 4: japanese patent No. 3534395

Patent document 5: japanese patent No. 4016483

Patent document 6: japanese patent No. 4078679

Patent document 7: international publication No. 2010/013651

Patent document 8: japanese patent No. 2675956

Patent document 9: japanese patent No. 3839829

Patent document 10: international publication No. 2014/129322

Patent document 11: international publication No. 2013/115071

Patent document 12: japanese patent laid-open publication No. 2018-119022

Patent document 13: japanese patent laid-open publication No. 2015-63586

Patent document 14: japanese patent No. 4406093

Patent document 15: japanese patent No. 3454024

Disclosure of Invention

Problems to be solved by the invention

The invention provides a dispersion liquid composition for ink which has excellent storage stability and also has excellent storage stability when prepared into ink, and an ink composition containing the dispersion liquid composition for ink.

Means for solving the problems

The inventors of the present application have made intensive studies to solve the above problems, and as a result, have completed the present invention described in the following 1) to 17).

1) A dispersion composition for ink, which contains a water-insoluble coloring agent, a water-soluble polysaccharide compound, a polyvalent metal salt, a dispersant and water.

2) The dispersion composition for ink according to 1), wherein the water-insoluble colorant contains at least one selected from the group consisting of a disperse dye and an oil-soluble dye.

3) The dispersion composition for ink according to 1) or 2), wherein the water-soluble polysaccharide compound contains at least one selected from the group consisting of alginic acid compounds, pectin compounds, carrageenan compounds, carboxymethyl cellulose compounds, and agar.

4) The dispersion composition for ink as set forth in any one of claims 1) to 3), wherein the polyvalent metal salt contains a salt of at least one metal selected from the group consisting of Ca, Mg, Ti, Al, Zn, Fe, Co, Ni, and Cu.

5) The dispersion composition for ink as set forth in any one of 1) to 4), wherein the dispersant contains at least one selected from the group consisting of an anionic dispersant, a nonionic dispersant, and a polymeric dispersant.

6) The dispersion composition for ink according to claim 5), wherein the anionic dispersant contains at least one selected from the group consisting of a formalin condensate of β -naphthalenesulfonate, a formalin condensate of alkylnaphthalenesulfonate, and a formalin condensate of creosote sulfonate.

7) The dispersion composition for ink according to claim 5) or 6), wherein the nonionic dispersant contains at least one selected from the group consisting of an ethylene oxide adduct of a phytosterol and an ethylene oxide adduct of a cholestanol.

8) The dispersion composition for ink as set forth in any one of claims 5) to 7), wherein the polymer dispersant contains a styrene- (meth) acrylic acid copolymer.

9) The dispersion composition for ink as set forth in any one of 1) to 8), further comprising an antifoaming agent.

10) The dispersion composition for ink as set forth in any one of 1) to 9), further comprising a water-soluble organic solvent.

11) The dispersion composition for ink as set forth in any one of 1) to 10), which further contains a preservative.

12) The dispersion composition for ink as set forth in any one of 1) to 11), which contains particles comprising the water-insoluble colorant, the water-soluble polysaccharide compound, and the polyvalent metal salt, and which have a number average particle diameter of 10 to 500 nm.

13) An ink composition comprising the dispersion composition for ink according to any one of 1) to 12).

14) An ink jet printing method, wherein the ink composition according to 13) is used as an ink, and droplets of the ink are attached to a recording medium by an ink jet printer to perform printing.

15) An inkjet printed material obtained by printing by the inkjet printing method according to 14).

16) A sublimation transfer dyeing method, wherein the inkjet printed material of 15) is heated to sublimation transfer the water-insoluble colorant applied to the inkjet printed material to a dyeing target material.

17) A sublimation transfer-dyed product obtained by dyeing according to the sublimation transfer-dyeing method described in 16).

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a dispersion composition for ink which has excellent storage stability and also has excellent storage stability when prepared into ink, and an ink composition containing the dispersion composition for ink.

Detailed Description

< Dispersion composition for ink >

The dispersion composition for ink according to the present embodiment contains a water-insoluble colorant, a water-soluble polysaccharide compound, a polyvalent metal salt, a dispersant, and water. The dispersion composition for ink according to the present embodiment has excellent storage stability, and also has excellent storage stability when prepared into ink. The reason for this is not clear, but the inventors of the present application presume as follows. That is, it is considered that the generally used anionic dispersant has a weak adsorption force to the water-insoluble colorant, and therefore has poor dispersion stability under thermal and secular conditions. In contrast, it is considered that the dispersion composition for ink according to the present embodiment utilizes aggregation of the water-soluble polysaccharide compound and the polyvalent metal salt to introduce the water-insoluble colorant into the aggregate, and as a result, the dispersion stability is improved.

Hereinafter, each component contained in the ink dispersion composition according to the present embodiment will be described in detail. Each component described below may be used alone or in combination of two or more.

[ Water-insoluble coloring agent ]

Examples of the water-insoluble coloring agent include dyes and pigments, and dyes are preferable.

Examples of the dye include direct dyes, vat dyes, sulfur dyes, disperse dyes, basic dyes, naphthol dyes, acid mordant dyes, oil-soluble dyes, reactive dyes, soluble vat dyes, sulfur vat dyes, and oxidation dyes. Specific examples of the dye include c.i. disperse yellow 3, 4, 5, 7, 8, 9, 13, 23, 24, 30, 33, 34, 39, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 114, 116, 118, 119, 122, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 186, 192, 198, 199, 200, 202, 204, 210, 211, 215, 216, 218, 224, 232, 237; c.i. disperse orange 1, 1: 1. 3,5, 7, 11, 13, 17, 20, 21, 23, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 47, 48, 49, 50, 53, 54, 55, 56, 57, 58, 59, 60, 61, 66, 71, 73, 76, 78, 80, 86, 89, 90, 91, 93, 96, 97, 118, 119, 127, 130, 139, 142; c.i. disperse reds 1,4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55: 1. 56, 58, 59, 60, 65, 70, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 158, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 283, 288, 298, 302, 303, 310, 323, 312, 320, 323, 324, 328, 359, 364; c.i. disperse violet 1,4, 8, 11, 17, 23, 26, 27, 28, 29, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, 77, 97; c.i. disperse green 9; c.i. disperse brown 1,2, 4, 9, 13, 19; c.i. disperse blue 3,5, 7,9, 14, 16, 19, 20, 26: 1. 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64: 1. 71, 72: 1. 73, 75, 77, 79: 1. 82, 83, 87, 91, 93, 94, 95, 64: 1. 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 131, 139, 141, 142, 143, 145, 146, 148, 149, 153, 154, 158, 165: 1. 165: 2. 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 266, 267, 270, 281, 284, 285, 287, 288, 291, 293, 295, 297, 301, 315, 330, 333, 341, 353, 354, 358, 359, 360, 364, 365, 366, 368; c.i. disperse black 1,3, 10, 24; c.i. solvent yellow 114; c.i. solvent orange 67; c.i. solvent red 146; c.i. solvent blue 36, 63, 83, 105, 111; c.i. reactive yellow 2, 3, 18, 81, 84, 85, 95, 99, 102; c.i. reactive orange 5, 9, 12, 13, 35, 45, 99; c.i. reactive brown 2, 8, 9, 17, 33; c.i. reactive red 3, 3: 1. 4, 13, 24, 29, 31, 33, 125, 151, 206, 218, 226; c.i. active violet 1, 24; c.i. reactive blue 2, 5, 10, 13, 14, 15: 1. 49, 63, 71, 72, 75, 162, 176; c.i. reactive green 5, 8, 19; c.i. reactive black 1, 8, 23, 39; c.i. acid yellow 1,3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 42, 44, 49, 59, 61, 65, 72, 73, 79, 99, 104, 110, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 220, 230, 232, 235, 241, 242, 246; c.i. acid orange 2, 3, 7, 8, 10, 19, 24, 51, 56, 67, 74, 80, 86, 87, 88, 89, 94, 95, 107, 108, 116, 122, 127, 140, 142, 144, 149, 152, 156, 162, 166, 168; c.i. acid brown 2,4, 13, 14, 19, 28, 44, 123, 224, 226, 227, 248, 282, 283, 289, 294, 297, 298, 301, 355, 357, 413; c.i. acid red 1,6, 8, 9, 13, 18, 27, 35, 37, 52, 54, 57, 73, 82, 88, 97, 106, 111, 114, 118, 119, 127, 131, 138, 143; c.i. acid violet 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126; c.i. acid blue 1, 7,9, 15, 23, 25, 40, 62, 72, 74, 80, 83, 90, 92, 103, 104, 112, 113, 114, 120, 127, 128, 129, 138, 140, 142, 156, 158, 171, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 220, 221, 224, 225, 229, 230, 239, 249, 258, 260, 264, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 350; c.i. acid green 9, 12, 16, 19, 20, 25, 27, 28, 40, 43, 56, 73, 81, 84, 104, 108, 109; c.i. acid black 1,2, 3, 24, 26, 31, 50, 52, 58, 60, 63, 107, 109, 112, 119, 132, 140, 155, 172, 187, 188, 194, 207, 222; c.i. direct yellow 2, 3, 4, 9, 10, 11, 12, 13, 15, 16, 50, 66, 73, 84, 86, 87, 88, 89, 91, 110, 127, 128, 129, 130, 132, 138, 139, 141, 142, 145; c.i. direct oranges 20, 25, 35, 38, 39, 41; c.i. direct brown 187, 195, 196, 202, 208, 209, 210, 213; c.i. direct red 76, 88, 89, 92, 101, 209, 220, 222, 224, 225, 226, 227, 234, 235, 238, 240, 243, 245, 247; c.i. direct blue 52, 55, 57, 76, 80, 84, 86, 87, 92, 102, 105, 106, 108, 110, 112, 197, 199, 200, 202, 205, 220, 231, 233, 235, 237, 238, 240, 245, 248, 250; c.i. direct green 55, 57, 59, 60, 77, 80, 82, 90; c.i. direct black 12, 19, 20, 22, 23, 105, 107, 110, 112, 115, 117, 120, 125, 129, 132, 135, 136; c.i. basic yellow 2, 3, 18, 21, 38, 40, 41, 43, 51, 63, 65, 67, 69; c.i. basic blue 2, 10, 37, 41, 43, 50, 55, 57, 60, 66, 69, 72, 75, 79; c.i. basic red 20, 25, 27, 29, 31, 45, 46, 47, 50; and so on.

Among these dyes, disperse dyes, oil-soluble dyes, and vat dyes are preferable, and specific examples thereof include c.i. disperse yellow 42, 49, 76, 83, 88, 93, 99, 119, 126, 160, 163, 165, 180, 183, 186, 198, 199, 200, 224, 237; c.i. disperse oranges 25, 29, 30, 31, 38, 42, 44, 45, 53, 54, 55, 71, 73, 80, 86, 96, 118, 119; c.i. disperse red 73, 88, 91, 92, 111, 127, 131, 143, 145, 146, 152, 153, 154, 179, 191, 192, 206, 221, 258, 283, 302, 323, 328, 359; c.i. disperse violet 26, 35, 48, 56, 77, 97; c.i. disperse blue 27, 54, 60, 73, 77, 79: 1. 87, 143, 165: 1. 165: 2. 181, 185, 197, 225, 257, 266, 267, 281, 341, 353, 354, 358, 360, 364, 365, 368; and so on. Examples of the dye having thermal transfer suitability (i.e., dye having sublimation property) include c.i. disperse yellows 51, 54, 60, 82, 232; c.i. disperse orange 5, 7, 20, 23, 25, 60; c.i. disperse red 4, 11, 50, 53, 59, 60, 239, 240, 364; c.i. disperse violet 8, 11, 17, 26, 27, 28, 36; c.i. disperse blue 3,5, 26, 35, 55, 56, 72, 81, 91, 108, 334, 359, 360, 366; c.i. disperse brown 27; c.i. solvent yellow 114; c.i. solvent orange 60, 67; c.i. solvent red 146; c.i. solvent blue 36, 63, 83, 105, 111; and so on.

The dispersion composition for ink according to the present embodiment preferably includes at least one selected from the group consisting of a disperse dye and an oil-soluble dye, more preferably includes at least one selected from the group consisting of a disperse dye having sublimation property and an oil-soluble dye having sublimation property, and further preferably includes at least one selected from the group consisting of c.i. disperse yellow 54, 232; c.i. disperse orange 25, 60; c.i. disperse red 60, 364; c.i. disperse violet 27, 28; and c.i. disperse blue 56, 72, 359, 360, 366; at least one of the group consisting of.

On the other hand, examples of the pigment include organic pigments and inorganic pigments, and organic pigments are preferable. Specific examples of the pigment include: c.i. pigment yellow 74, 120, 128, 138, 151, 185, 217; c.i. pigment orange 13, 16, 34, 43; c.i. pigment red 122, 146, 148; c.i. pigment violet 19, 23; c.i. pigment blue 15, 15: 1. 15: 2. 15: 3. 15: 4. 15: 5. 15: 6; c.i. pigment green 7, 8; and so on.

The water-insoluble colorant may be a dry colorant in powder or cake form, or may be a wet cake (wet cake) or slurry. In addition, a dispersant such as a surfactant may be contained in a small amount for the purpose of suppressing aggregation of the colorant particles during or after the synthesis of the colorant. Commercially available water-insoluble colorants are available in grades for industrial dyeing, resin dyeing, inks, toners (toners), inkjet inks, and the like, and the production method, purity, particle size, and the like are different from each other. In order to suppress aggregation after pulverization, the particles are preferably smaller, and in view of the influence on dispersion stability and ink ejection accuracy, it is preferable that the amount of impurities is as small as possible.

Two or more kinds of water-insoluble coloring agents may be used in combination. For example, when the color is black, the color is adjusted to black by using a blue dye as a main component and appropriately combining an orange dye and a red dye, and the blue dye can be used as a black dye. In addition, a plurality of dyes may be used in combination for the purpose of fine-tuning the color tone of blue, orange, red, purple, black, or the like.

The content of the water-insoluble coloring agent varies depending on the kind of the water-insoluble coloring agent to be used, the kind of the solvent or the dispersant, and the like, and is not particularly limited. The total content of the water-insoluble colorant is usually 0.1 to 25% by mass, preferably 0.5 to 20% by mass, and more preferably 1 to 15% by mass, based on the total amount of the ink dispersion composition. When the content of the water-insoluble coloring agent is 0.1% by mass or more, the color developing concentration tends to be sufficient. Further, by setting the content of the water-insoluble colorant to 25% by mass or less, the storage stability of the ink dispersion composition tends to be good.

[ Water-soluble polysaccharide Compound ]

As the water-soluble polysaccharide compound, a water-soluble polysaccharide compound having a carboxyl group can be preferably used. The water-soluble polysaccharide compound may have 1 carboxyl group, 2 or more carboxyl groups, and a functional group other than a carboxyl group in its structure. When the water-soluble polysaccharide compound has 2 or more carboxyl groups, a part thereof may be substituted with another substituent.

Examples of the water-soluble polysaccharide compound include alginic acid compounds, pectin compounds, carrageenan compounds, carboxymethyl cellulose compounds, and agar. Examples of alginic acid compounds include: alginic acid; alginate compounds such as potassium alginate, sodium alginate, ammonium alginate, and alginic acid ester; and so on. Examples of the pectin-based compound include polysaccharides formed from linear polymers of D-galacturonic acid. A polysaccharide in which some of the carboxyl groups of D-galacturonic acid are methyl esters may be used as long as it has carboxyl groups. Examples of the carrageenan-based compound include kappa carrageenan, iota carrageenan and the like.

Among these water-soluble polysaccharide compounds, at least one selected from the group consisting of alginic acid compounds, carrageenan compounds, and pectin compounds is preferably contained from the viewpoint of easy gelation by a polyvalent metal salt described later, more preferably at least one selected from the group consisting of sodium alginate, kappa-carrageenan, and pectin, and still more preferably sodium alginate.

Sodium alginate is available in various forms depending on its structure, degree of polymerization, etc., and known compounds can be used. Further, sodium alginate may be commercially available. Examples of commercially available products include: sodium alginate (pure chemical products); kimica Algin ULV-L3, Kimica Algin ULV-L3, SKAT-ULV, Kimica Algin IL-2 (all Kimica products); and so on.

The content of the water-soluble polysaccharide compound is not particularly limited, and varies depending on the molecular weight of the water-soluble polysaccharide compound to be used. The total content of the water-soluble polysaccharide compound is usually 0.01 to 1.0% by mass, preferably 0.05 to 1.0% by mass, and more preferably 0.1 to 0.8% by mass, based on the total amount of the ink dispersion composition. When the content of the water-soluble polysaccharide compound is 0.01% by mass or more, the degree of gelation tends to be sufficient. Further, when the content of the water-soluble polysaccharide compound is 1.0% by mass or less, the decrease in storage stability due to thickening tends to be suppressed.

[ polyvalent Metal salt ]

The polyvalent metal salt is used for the purpose of crosslinking the water-soluble polysaccharide compound. Examples of the polyvalent metal salt include salts of at least one metal selected from the group consisting of Ca, Mg, Ti, Al, Zn, Fe, Co, Ni, and Cu. The anion forming the polyvalent metal salt is not particularly limited, and may be an inorganic anion such as a halide ion, a hydroxide ion, a sulfate ion, or a nitrate ion, or an organic anion such as acetic acid, lactic acid, or formic acid. The polyvalent metal salt may be an oxide which is decomposed or dissolved after being added to the dispersion composition for ink.

Specific examples of the polyvalent metal salt include a chloride containing a divalent metal ion, a hydroxide containing a divalent metal ion, a sulfate containing a divalent metal ion, a nitrate containing a divalent metal ion, and the like. Specific examples thereof include calcium chloride, calcium chloride dihydrate, calcium chloride tetrahydrate, calcium chloride hexahydrate, calcium sulfate dihydrate, calcium lactate, calcium hydroxide, calcium nitrate tetrahydrate, calcium acetate, magnesium fluoride, magnesium acetate, magnesium bromide, magnesium formate, magnesium nitrate, magnesium sulfate, titanium chloride, titanium iodide, aluminum chloride, aluminum oxide, aluminum bromide, aluminum iodide, aluminum sulfate, aluminum nitrate, zinc chloride, zinc bromide, ferric chloride, cobalt chloride, nickel chloride, copper chloride, lead sulfate, lead hydroxide, lead nitrate, and copper sulfate.

The content of the polyvalent metal salt is not particularly limited, and varies depending on the type of the polyvalent metal salt or the water-soluble polysaccharide compound to be used. The total content of the polyvalent metal salt is usually 0.01 to 10% by mass, preferably 0.02 to 8% by mass, and more preferably 0.04 to 5% by mass, based on the total amount of the ink dispersion composition. When the content of the polyvalent metal salt is 0.01% by mass or more, the degree of gelation tends to be sufficient. Further, when the content of the polyvalent metal salt is 10% by mass or less, the decrease in storage stability due to thickening tends to be suppressed.

[ particles comprising a Water-insoluble coloring agent, a Water-soluble polysaccharide Compound, and a polyvalent Metal salt ]

The ink dispersion composition according to the present embodiment preferably contains particles containing the above-described water-insoluble colorant, water-soluble polysaccharide compound, and polyvalent metal salt. By including the particles in the ink dispersion composition, the ejection stability when the ink is prepared tends to be improved.

The number average particle diameter of the particles is preferably 10 to 500nm, more preferably 10 to 300 nm. The maximum particle diameter of the particles is preferably 900nm or less. By setting the number average particle diameter to 500nm or less and the maximum particle diameter to 900nm or less, the occurrence of clogging can be suppressed and stable discharge can be achieved even in an ink jet textile printing method in which discharge is performed from a fine nozzle. Further, when the number average particle diameter is 10nm or more, the particles are likely to be inhibited from aggregating and settling to clog a nozzle or a filter. The number average particle diameter can be determined by a commercially available particle diameter measuring machine using a light scattering method, an electrophoresis method, a laser doppler method, or the like.

[ dispersing agent ]

The dispersant preferably contains at least one selected from the group consisting of an anionic dispersant, a nonionic dispersant, and a polymer dispersant.

Examples of the anionic dispersant include formalin condensates of polymeric sulfonic acids (preferably aromatic sulfonic acids), lignin sulfonic acids, formalin condensates of lignin sulfonic acids, salts thereof, or mixtures thereof (hereinafter, unless otherwise specified, "formalin condensates of sulfonic acids" includes salts and mixtures), formalin condensates of alkylnaphthalene sulfonates, and the like. Examples of the salt include sodium salt, potassium salt, and lithium salt. Examples of the formalin condensate of an aromatic sulfonic acid include: creosote sulfonic acid; cresol sulfonic acid; phenolsulfonic acid; beta-naphthalenesulfonic acid; beta-naphthol sulfonic acid; a mixture of beta-naphthalenesulfonic acid and beta-naphtholsulfonic acid; a mixture of cresolsulfonic acid and 2-naphthol-6-sulfonic acid; (ii) lignosulfonic acid; and the like formalin condensates. Among these, formalin condensates of creosote sulfonic acid, β -naphthalenesulfonic acid, and lignin sulfonic acid are preferable.

The anionic dispersant is also available as a commercially available product. Examples of the formalin condensate of β -naphthalenesulfonic acid include delmol N (manufactured by kao corporation) and LAVELIN W series (manufactured by first industrial pharmaceutical co. Examples of the formalin condensate of creosol sulfonic acid include Demol C (manufactured by Kao corporation). As the formalin condensate of a specific aromatic sulfonic acid, Demol SN-B (manufactured by Kao corporation) and the like can be mentioned. Examples of the formalin condensate of methylnaphthalenesulfonic acid include LAVELIN AN series (first industrial pharmaceutical company). Among these, the Demol N, LAVELIN AN series and LAVELIN W series are preferable, the Demol N and LAVELIN W series are more preferable, and the LAVELIN W series is further preferable. Examples of the lignosulfonic acid include vanilex N, vanilex RN, vanilex G, and perrallex DP (all manufactured by japan paper company). Among these, VANILLEX RN, VANILLEX N and VANILLEX G are preferable.

Examples of the nonionic dispersant include Ethylene Oxide (EO) adducts of phytosterols and Ethylene Oxide (EO) adducts of cholestanols. In the present specification, "phytosterols" are used in a sense including both "phytosterols" and "hydrogenated phytosterols". Examples of the ethylene oxide adducts of phytosterols include ethylene oxide adducts of phytosterols and ethylene oxide adducts of hydrogenated phytosterols. Similarly, in the present specification, "cholestanol" is used in a sense including both "cholestanol" and "hydrogenated cholestanol". Examples of the ethylene oxide adduct of a cholestanol include an ethylene oxide adduct of cholestanol and an ethylene oxide adduct of hydrogenated cholestanol. The addition amount of ethylene oxide per 1 mole of the phytosterol or the cholestane is preferably about 10 to 50 moles, and HLB is preferably about 13 to 20.

The nonionic dispersant is also commercially available. Examples of the ethylene oxide adduct of a phytosterol include NIKKOL BPS-20, NIKKOL BPS-30 (both EO adducts of phytosterols available from Sun-light chemical Co., Ltd.), and NIKKOL BPSH-25 (EO adducts of hydrogenated phytosterols available from Sun-light chemical Co., Ltd.). Examples of the ethylene oxide adduct of a cholestanol include NIKKOL DHC-30 (EO adduct of cholestanol, manufactured by Nikkol chemical Co., Ltd.).

The polymer dispersant is preferably a dispersant used in inkjet inks and the like, and a copolymer polymer having a hydrophilic portion and a hydrophobic portion in the molecule is preferable. Specific examples thereof include acrylic dispersants such as styrene-acrylic acid copolymers, styrene-acrylic acid-acrylate copolymers, styrene-methacrylic acid copolymers, and styrene-methacrylic acid-acrylate copolymers; maleic acid-based dispersants such as styrene-maleic acid copolymers, acrylic ester-maleic acid copolymers, and styrene-acrylic ester-maleic acid copolymers; sulfonic acid dispersants such as acrylate-styrenesulfonic acid copolymers, styrene-methacrylic acid sulfonic acid copolymers, and acrylate-allylsulfonic acid copolymers; polyester dispersants such as polyester-acrylic acid copolymers, polyester-acrylic acid-acrylate copolymers, polyester-methacrylic acid copolymers, and polyester-methacrylic acid-acrylate copolymers; or salts thereof, and the like.

Among these polymeric dispersants, styrene- (meth) acrylic acid copolymers are preferred. The styrene- (meth) acrylic acid copolymer is a copolymer of a styrene monomer and a (meth) acrylic acid monomer. Specific examples of the copolymer include an (α -methyl) styrene-acrylic acid copolymer, an (α -methyl) styrene-acrylic acid-acrylate copolymer, an (α -methyl) styrene-methacrylic acid-acrylate copolymer, an (α -methyl) styrene-acrylate-maleic acid (anhydride) copolymer, an acrylate-styrene sulfonic acid copolymer, and an (α -methyl) styrene-methacrylic acid sulfonic acid copolymer. In the present specification, "(meth) acrylic acid" is used in a meaning including "acrylic acid" and "methacrylic acid". In addition, "(α -methyl) styrene" is used in a meaning including "α -methylstyrene" and "styrene".

The mass average molecular weight of the styrene- (meth) acrylic acid copolymer is, for example, preferably 1000 to 20000, more preferably 2000 to 19000, and still more preferably 4000 to 17000. When the mass average molecular weight is 1000 or more, the dispersion stabilizing ability for the water-insoluble coloring agent tends to be improved. In addition, when the mass average molecular weight is 20000 or less, the following tendency is present: the ability to disperse the water-insoluble coloring agent is improved, and thickening can be suppressed. The mass average molecular weight of the styrene- (meth) acrylic acid copolymer can be measured by a GPC (gel permeation chromatography) method.

The acid value of the styrene- (meth) acrylic acid copolymer is, for example, preferably 50 to 250mgKOH/g, more preferably 100 to 250mgKOH/g, and still more preferably 150 to 250 mgKOH/g. When the acid value is 50mgKOH/g or more, the following tendency is exhibited: the water-insoluble coloring agent has improved solubility in water and improved dispersion-stabilizing ability against water-insoluble coloring agents. Further, when the acid value is 250mgKOH/g or less, bleeding tends to occur in an image after printing due to an increase in affinity with an aqueous medium. The acid value of the resin is a mg number of KOH required for neutralizing 1g of the resin, and can be measured in accordance with JIS-K3054.

The glass transition temperature of the styrene- (meth) acrylic acid copolymer is, for example, preferably 45 to 135 ℃, more preferably 55 to 120 ℃, and still more preferably 60 to 110 ℃.

The styrene- (meth) acrylic acid copolymer is also commercially available. Specific examples thereof include Joncryl 67, 586, 611, 678, 680, 682, 683, 690, 52J, 57J, 60J, 63J, 70J, JDX-6180, HPD-196, HPD96J, PDX-6137A, 6610, JDX-6500, JDX-6639, and PDX-6102B, PDX-6124 (both manufactured by BASF corporation). Of these, Joncryl 67 (mass average molecular weight: 12500, acid value: 213mgKOH/g), 678 (mass average molecular weight: 8500, acid value: 215mgKOH/g), 682 (mass average molecular weight: 1700, acid value: 230mgKOH/g), 683 (mass average molecular weight: 4900, acid value: 215mgKOH/g), 690 (mass average molecular weight: 16500, acid value: 240mgKOH/g) are preferred.

The dispersant may further include at least one selected from the group consisting of a cationic dispersant and an amphoteric dispersant. Examples of the cationic dispersant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium chloride salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Examples of the amphoteric dispersant include carboxybetaines, sulfobetaines, aminocarboxylates, imidazolinium betaines, and the like.

Examples of the dispersant other than those described above include copolymers (block copolymers, random copolymers, graft copolymers, and the like) formed from at least 2 monomers (at least one of which is a hydrophilic or water-soluble monomer) selected from styrene and its derivatives, vinylnaphthalene and its derivatives, aliphatic alcohol esters of α, β -ethylenically unsaturated carboxylic acids, acrylic acid and its derivatives, maleic acid and its derivatives, itaconic acid and its derivatives, fumaric acid and its derivatives, vinyl acetate, vinyl alcohol, vinylpyrrolidone, acrylamide, and the like, and salts thereof.

The total content of the dispersant is usually 1 to 120% by mass, preferably 10 to 100% by mass, and more preferably 20 to 80% by mass, based on the total amount of the water-insoluble colorant.

[ Water ]

The water is preferably water containing a small amount of impurities, such as ion-exchanged water and distilled water.

[ other ingredients ]

The ink dispersion composition according to the present embodiment may further contain an antifoaming agent. The defoaming agent has an action of reducing the foam in the solution or suppressing the foam itself, and examples thereof include an oily substance (higher alcohol and the like) having low volatility and high diffusibility, a nonionic surfactant described later, and the like. Specific examples thereof include high-oxidation oil-based, glycerin fatty acid ester-based, fluorine-based, and silicone-based compounds.

The ink dispersion composition according to the present embodiment may further contain a water-soluble organic solvent. Examples of the water-soluble organic solvent include: C1-C4 alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, and tert-butanol; carboxamides such as N, N-dimethylformamide and N, N-dimethylacetamide; lactams such as 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, and N-methylpyrrolidin-2-one; cyclic ureas such as 1, 3-dimethylimidazolidin-2-one and 1, 3-dimethylhexahydropyrimidin-2-one; ketones or ketone alcohols such as acetone, methyl ethyl ketone, and 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran and dioxane; mono-, oligo-, or polyalkylene glycols or thioglycols having a C2-C6 alkylene unit such as ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butylene glycol, 1, 4-butylene glycol, 1, 6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiethylene glycol, dithiodiethylene glycol, etc.; polyhydric alcohols (preferably triols) such as trimethylolpropane, glycerol, hexane-1, 2, 6-triol and the like; C1-C4 alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; gamma-butyrolactone; dimethyl sulfoxide; and so on.

The water-soluble organic solvent also includes substances that are solid at ordinary temperature, such as trimethylolpropane, and these substances are also water-soluble when they are solid, and can be used for the same purpose as the water-soluble organic solvent when they are dissolved in water. Therefore, the present specification is described in the category of water-soluble organic solvents.

The ink dispersion composition according to the present embodiment may further contain an antiseptic agent. Examples of the preservative include compounds of organic sulfur, organic nitrogen sulfur, organic halogen, halogenated allyl sulfone, iodopropynyl, N-halogenated alkyl sulfide, nitrile, pyridine, 8-hydroxyquinoline, benzothiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, aniline, adamantane, dithiocarbamate, bromoindanone, benzyl bromoacetate, and inorganic salt. Specific examples of the organic halogen-based compound include sodium pentachlorophenolate and the like. Specific examples of the pyridine oxide compound include 2-pyridinethiol-1-sodium oxide and the like. Specific examples of the isothiazolin-based compound include 1, 2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, and 2-methyl-4-isothiazolin-3-one calcium chloride. Specific examples of the other preservatives include anhydrous sodium acetate, sodium sorbate, sodium benzoate, and Proxel GXL (S) and Proxel XL-2(S) which are trade names manufactured by Lonza.

The ink dispersion composition according to the present embodiment may further contain an ink preparation agent such as a pH adjuster, a chelating agent, a rust inhibitor, a water-soluble ultraviolet absorber, a water-soluble polymer compound, a dye dissolving agent, an antioxidant, and a surfactant.

Examples of the pH adjuster include: alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonium hydroxide (ammonia); carbonates of alkali metals such as lithium carbonate, sodium hydrogen carbonate, and potassium carbonate; alkali metal salts of organic acids such as potassium acetate; inorganic bases such as sodium silicate and disodium phosphate; and so on.

Examples of the chelating agent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracil diacetate.

Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and the like.

Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamine, and polyimine.

Examples of the dye dissolving agent include urea, epsilon-caprolactam, and ethylene carbonate.

Examples of the antioxidant include organic antioxidants such as hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles; metal complex antioxidants such as nickel complexes and zinc complexes; and so on.

Examples of the surfactant include known surfactants such as anionic, cationic, amphoteric, nonionic, silicone, and fluorine surfactants.

Examples of the anionic surfactant include alkylsulfonates, alkylcarboxylates, α -olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acylamino acids and salts thereof, N-acyl methyltaurates, alkylsulfate polyoxyalkyl ether sulfates, alkylsulfate polyoxyethylene alkyl ether phosphates, rosin acid soaps, castor oil sulfate salts, lauryl alcohol sulfate salts, alkylphenol phosphate esters, alkyl phosphate esters, alkylaryl sulfonates, diethyl sulfosuccinates, diethyl hexyl sulfosuccinates, and dioctyl sulfosuccinates. Examples of commercially available products include HITENOL LA-10, LA-12, LA-16, NEOHITENOL ECL-30S, ECL-45, all of which are manufactured by first Industrial pharmaceutical Co.

Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

Examples of the amphoteric surfactant include lauryl dimethyl glycine betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, coconut oil fatty acid amide propyl dimethyl glycine betaine, poly octyl poly aminoethyl glycine, imidazoline derivatives, and the like.

Examples of the nonionic surfactant include ether-based surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether; esters such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, and polyoxyethylene stearate; acetylene glycol (alcohol) systems such as 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, 3, 6-dimethyl-4-octyne-3, 6-diol, and 3, 5-dimethyl-1-hexyne-3-ol; surfynol 104, 105, 82, 465, Olfine STG manufactured by Air Products Japan; polyglycol ether systems (e.g., Tergitol 15-S-7 manufactured by SIGMA-ALDRICH Co., Ltd.); and so on.

Examples of the silicone surfactant include polyether-modified silicone and polyether-modified polydimethylsiloxane. Examples of commercially available products include BYK347 (polyether-modified siloxane) manufactured by BYK Chemie; BYK345, BYK348 (polyether-modified polydimethylsiloxane), and the like.

Examples of the fluorine-based surfactant include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain. Examples of commercially available products include Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30 and FS-31 (manufactured by DuPont Co., Ltd.); PF-151N, PF-154N (manufactured by OMNOVA Inc.); and so on.

[ method for producing Dispersion composition for ink ]

The ink dispersion composition according to the present embodiment can be prepared by the following 2 methods, for example.

(preparation method 1)

In the preparation method 1, a dispersion liquid containing a water-insoluble coloring agent, a water-soluble polysaccharide compound and water is mixed and dispersed with a dispersion liquid containing a dispersant, a defoaming agent, a preservative and water, and then the dispersion liquid is mixed and dispersed with an aqueous solution containing a polyvalent metal salt to obtain a dispersion liquid composition for ink.

More specifically, a dispersion liquid containing a water-insoluble coloring agent, a water-soluble polysaccharide compound and water, and a dispersion liquid containing a dispersant, an antifoaming agent, a preservative and water were mixed, and glass beads were added to the resulting mixture liquid, followed by dispersion treatment for about 15 hours under water cooling using a sand mill. In the dispersion treatment, a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, or the like may be used in addition to the sand mill (bead mill). The dispersing time is not particularly limited, but is preferably set so that the number average particle diameter of the water-insoluble coloring agent is 10 to 500 nm. By setting the number average particle diameter to 10 to 500nm, the dispersion stability and storage stability of the ink dispersion composition tend to be reduced. In this case, the phenomenon can be suppressed by adding an ink preparation agent such as a water-soluble organic solvent or a surfactant. Further, a defoaming agent such as a silicone-based or an acetylene alcohol-based defoaming agent may be added at the time of preparation of the dispersion, if necessary. However, as the defoaming agent, there is also a defoaming agent that suppresses dispersion and micronization of dyes and the like, it is preferable to use a defoaming agent that does not affect micronization, stability of the dispersion liquid, and the like. Preferred examples of the defoaming agent include: olfine series (SK-14, etc.) manufactured by Nissan chemical industries, Ltd.; surfynol series (104, DF-110D, etc.) manufactured by Air Products Japan; and so on.

After the dispersion treatment, an aqueous solution containing a polyvalent metal salt is added, and the dispersion treatment is similarly performed for about 2 hours. Then, the dispersion was filtered through a glass fiber filter paper GC-50 (manufactured by Toyo Filter paper Co., Ltd., pore diameter: 0.5 μm) to remove components having large particle sizes, thereby obtaining an ink dispersion composition.

(preparation method 2)

In the case of the preparation method 2, the two dispersions were mixed to obtain a dispersion composition for ink.

The method for preparing the dispersion of claim 1 includes, for example, the following methods. First, a dispersion liquid containing a water-soluble polysaccharide compound and water, and a dispersion liquid containing a dispersant, an antifoaming agent, a preservative and water were mixed, glass beads were added to the obtained mixed liquid, and dispersion treatment was performed for about 15 hours under water cooling using a sand mill. In the dispersion treatment, a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, or the like may be used in addition to the sand mill (bead mill). The dispersing time is not particularly limited, but is preferably set so that the number average particle diameter of the water-soluble polysaccharide compound is 10 to 500 nm. By setting the number average particle diameter to 10 to 500nm, the dispersion stability and storage stability of the ink dispersion composition tend to be reduced. In this case, the ink preparation agent such as a water-soluble organic solvent or a surfactant may be added to suppress this phenomenon. Further, a defoaming agent such as a silicone-based or an acetylene alcohol-based defoaming agent may be added at the time of preparation of the dispersion, if necessary. However, as the defoaming agent, there is also a defoaming agent that suppresses dispersion and micronization of dyes and the like, it is preferable to use a defoaming agent that does not affect micronization, stability of the dispersion liquid, and the like. Preferable examples of the defoaming agent include Olfine series (SK-14, etc.) manufactured by Nissan chemical industries, Ltd.; surfynol series (104, DF-110D, etc.) manufactured by Air Products Japan; and so on.

After the dispersion treatment, an aqueous solution containing a polyvalent metal salt is added, and the dispersion treatment is similarly performed for about 2 hours. Next, the dispersion was filtered through a glass fiber filter GC-50 (manufactured by Toyo Filter paper Co., Ltd., pore diameter: 0.5 μm) to remove components having a large particle size, thereby obtaining a 1 st dispersion.

On the other hand, as a method for preparing the 2 nd dispersion, for example, the following method can be mentioned. First, glass beads were added to a dispersion liquid containing a water-insoluble coloring agent, a dispersant, an antifoaming agent, a preservative and water, and dispersion treatment was performed for about 15 hours under water cooling using a sand mill. In the dispersion treatment, a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, or the like may be used in addition to the sand mill (bead mill). The dispersing time is not particularly limited, but is preferably set so that the number average particle diameter of the water-insoluble coloring agent is 10 to 500 nm. By setting the number average particle diameter to 10 to 500nm, the dispersion stability and storage stability of the ink dispersion composition tend to be reduced. In this case, the ink preparation agent such as a water-soluble organic solvent or a surfactant may be added to suppress this phenomenon. Further, a defoaming agent such as a silicone-based or an acetylene alcohol-based defoaming agent may be added at the time of preparation of the dispersion, if necessary. However, as the defoaming agent, there is also a defoaming agent that suppresses dispersion and micronization of dyes and the like, it is preferable to use a defoaming agent that does not affect micronization, stability of the dispersion liquid, and the like. Preferred examples of the defoaming agent include: olfine series (SK-14, etc.) manufactured by Nissan chemical industries, Ltd.; surfynol series (104, DF-110D, etc.) manufactured by Air Products Japan; and so on.

After the dispersion treatment, an aqueous solution containing a polyvalent metal salt is added, and the dispersion treatment is similarly carried out for about 2 hours. Next, the dispersion was filtered through a glass fiber filter GC-50 (manufactured by Toyo Filter paper Co., Ltd., pore diameter: 0.5 μm) to remove components having a large particle size, thereby obtaining a2 nd dispersion.

Then, the 1 st dispersion and the 2 nd dispersion are mixed to obtain a dispersion composition for ink. Examples of the mixing method include: a method of adding the 2 nd dispersion to the 1 st dispersion and dispersing; a method of mixing the two dispersions while stirring; and so on.

The dispersion composition for ink according to the present embodiment is less likely to cause aggregation, precipitation, and the like of solids even after long-term storage, and has excellent storage stability with little change in physical properties such as viscosity, average particle diameter, and the like. The ink composition using the dispersion composition for ink according to the present embodiment is excellent not only in color developability but also in various fastness properties such as light fastness, rubbing resistance, gas fastness, chlorine fastness, perspiration fastness, and washing fastness of printed matter.

< ink composition >

The ink composition according to the present embodiment contains the dispersion composition for ink according to the present embodiment described above.

Examples of the method for producing the ink composition include a method of mixing the dispersion composition for ink according to the present embodiment, a water-soluble organic solvent, water, and, if necessary, an ink preparation agent. The order in which they are mixed is not particularly limited.

The content of the dispersion composition for ink is, for example, 2 to 40% by mass, preferably 3 to 35% by mass, and more preferably 5 to 35% by mass, based on the total amount of the ink composition. In this case, the content of the water-insoluble colorant is adjusted to be 0.3 to 10 mass% based on the total amount of the ink composition. The total content of the water-soluble organic solvent is usually 5 to 50% by mass, preferably 10 to 50% by mass, more preferably 10 to 30% by mass, and still more preferably 10 to 20% by mass, based on the total amount of the ink composition. The total content of the ink preparation agent is usually 0 to 25% by mass, preferably 0.01 to 20% by mass, based on the total amount of the ink composition.

The preparation of the ink composition may be followed by microfiltration using a membrane filter or the like. In particular, when the ink composition is used as an inkjet ink, microfiltration is preferably performed for the purpose of preventing clogging of nozzles and the like. The pore diameter of the filter used for the microfiltration is usually 0.1 to 1 μm, preferably 0.1 to 0.8. mu.m.

The ink composition according to the present embodiment preferably has a pH of 5 to 11 at 25 ℃, more preferably a pH of 7 to 10, from the viewpoint of improving storage stability.

The viscosity of the ink composition according to the present embodiment at 25 ℃ is preferably about 3 to 20mPa · s when measured with an E-type viscometer from the viewpoint of ejection response at high speed. The ink composition of the present embodiment preferably has a surface tension of about 20 to 45mN/m as measured by a plate method at 25 ℃. In practice, the ink jet printer is adjusted to have appropriate physical property values in consideration of the ejection amount, response speed, ink droplet flight characteristics, and the like of the ink jet printer to be used.

The ink composition according to the present embodiment can be used in various fields, and is suitable for water-based inks for writing, water-based printing inks, information recording inks, textile printing, and the like. The ink composition according to the present embodiment is preferably used as an inkjet ink, particularly an inkjet ink for textile printing.

The ink composition according to the present embodiment may be combined with other ink compositions to form an ink set. For example, the ink composition according to the present embodiment may be combined with at least one ink composition selected from the group consisting of a yellow ink composition, a magenta ink composition, and a cyan ink composition to form an ink set.

< ink jet printing method and ink jet printed article, and sublimation transfer dyeing method and sublimation transfer dyed article >

The inkjet printing method according to the present embodiment is a method of printing by using the ink composition according to the present embodiment as an ink and attaching droplets of the ink to a recording medium by an inkjet printer, and the inkjet printed material according to the present embodiment is obtained by printing by the inkjet printing method according to the present embodiment.

The recording medium is not particularly limited as long as printing can be performed based on the ink composition according to the present embodiment. As an example of a preferable recording medium, a fiber containing a hydrophobic resin is exemplified. When the inkjet printed material is used in a sublimation transfer dyeing method described later, an intermediate recording medium described later can be given as an example of a preferable recording medium.

In the sublimation transfer dyeing method according to the present embodiment, the inkjet printed material according to the present embodiment is heated to sublimation transfer the water-insoluble colorant added to the inkjet printed material to the object to be dyed, and the sublimation transfer dyed material according to the present embodiment is dyed by the sublimation transfer dyeing method according to the present embodiment.

The object to be dyed is not particularly limited as long as it can be dyed with the water-insoluble colorant contained in the ink composition according to the present embodiment. Examples of preferable objects to be dyed include those selected from fibers, films, and sheets containing hydrophobic resins.

The inkjet printing method and the sublimation transfer dyeing method according to the present embodiment are preferably used when printing hydrophobic fibers. Hereinafter, the details of the printing of the hydrophobic fibers will be described.

[ fibers, films, and sheets containing hydrophobic resins ]

Examples of the hydrophobic resin include resins such as polyester, nylon, triacetate, diacetate, and polyamide, and resins containing two or more of these resins. Examples of the fibers containing the hydrophobic resin include fibers made of the hydrophobic resin, and blended fibers of these fibers and regenerated fibers such as rayon, and natural fibers such as kapok, silk, and wool. Among the fibers, fibers having an ink-receiving layer (barrier layer) are also known, and such fibers may also be used. The fiber having the ink-receiving layer can be produced by a known method, and can be obtained as a commercially available product. The material, structure, and the like of the ink-receiving layer are not particularly limited, and may be appropriately used according to the purpose and the like. Examples of the fabric as a structure of fibers containing a hydrophobic resin include satin, flat woven fabric (tropical), double-faced embossed fabric, microfiber, and the like.

Examples of the film or sheet containing a hydrophobic resin include: polyethylene terephthalate films, polyethylene terephthalate sheets; a fabric, glass, metal, or ceramic coated with a hydrophobic resin; and so on.

[ printing method of hydrophobic fiber ]

Printing methods of hydrophobic fibers are roughly classified into direct printing methods and sublimation transfer printing methods.

(direct printing method)

The direct printing method includes the following steps: a printing step of forming a recorded image such as characters and patterns by using an ink composition as an ink and causing droplets of the ink to adhere to fibers containing a hydrophobic resin by an ink jet printer; a fixing step of fixing the water-insoluble colorant in the droplets of the ink adhering in the printing step to the fibers by heat; and a washing step of washing the unfixed water-insoluble coloring agent remaining in the fibers.

The fixing process is generally performed by known steaming or baking. Examples of steaming include the following: the fibers are treated with high-temperature steam at a temperature of usually 170 to 180 ℃ for about 10 minutes, or treated with high-pressure steam at a temperature of usually 120 to 130 ℃ for about 20 minutes, respectively, to thereby color the water-insoluble coloring agent on the fibers (also referred to as wet heat fixing). Examples of the baking (hot melt adhesive) include the following methods: the fiber is treated at 190 to 210 ℃ for about 60 to 120 seconds to color the fiber with the dye (also referred to as dry heat fixing).

The washing step is a step of washing the obtained fibers with warm water and water added as needed. The warm water or water used for washing may contain a surfactant. It is also preferable to dry the washed fiber at 50 to 120 ℃ for 5 to 30 minutes.

The direct printing method may further include a pretreatment process of the fiber for the purpose of preventing penetration and the like. Examples of the pretreatment step include the following steps: an aqueous solution (pretreatment solution) containing at least a paste and, if necessary, an alkaline substance, an anti-reducing agent and a hydrotropic agent is applied to the fibers before the ink is attached.

Examples of the paste include natural gums such as guar gum and locust bean; starches; marine algae such as sodium alginate and Gloiopeltis furcata; plant skins such as pectic acid; cellulose derivatives such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose; processing starches such as carboxymethyl starch; synthetic pastes such as polyvinyl alcohol and polyacrylate, and sodium alginate is preferred.

Examples of the basic substance include alkali metal salts of inorganic acids or organic acids; salts of alkaline earth metals; and compounds which liberate a base when heated, and the like, and alkali metal hydroxides and alkali metal salts are preferred. Specific examples thereof include alkali metal hydroxides such as sodium hydroxide and calcium hydroxide; alkali metal salts of inorganic compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, and sodium phosphate; alkali metal salts of organic compounds such as sodium formate and sodium trichloroacetate; and the like, sodium bicarbonate is preferred.

As the anti-reducing agent, sodium m-nitrobenzenesulfonate is preferable.

The hydrotrope includes ureas such as urea and dimethylurea, and urea is preferable.

The paste, the alkaline substance, the anti-reducing agent and the hydrotrope may be used singly or in combination of two or more.

The mixing ratio of the components in the pretreatment liquid is, for example, 0.5 to 5% by mass of the paste, 0.5 to 5% by mass of the sodium bicarbonate, 0 to 5% by mass of the sodium m-nitrobenzenesulfonate, 1 to 20% by mass of the urea, and the balance of water.

As a method for attaching the pretreatment liquid to the fiber, for example, a padding method is exemplified. The squeezing rate of pad dyeing is preferably about 40 to 90%, more preferably about 60 to 80%.

(sublimation transfer dyeing method)

The sublimation transfer printing dyeing method comprises the following steps: a printing step of forming a recording image such as characters and patterns by using an ink composition as an ink and causing droplets of the ink to adhere to an intermediate recording medium by an ink jet printer; and a transfer step of bringing the surface of the intermediate recording medium to which the ink has adhered into contact with a substance selected from the group consisting of fibers, films and sheets containing a hydrophobic resin, and sublimation-transferring the water-insoluble coloring agent in the droplets of the ink adhered to the intermediate recording medium to the substance by heat treatment.

The heat treatment in the transfer step may be a dry heat treatment usually at about 190 to 200 ℃.

As the intermediate recording medium, the following media are preferable: the water-insoluble colorant in the droplets of the ink adhering to the intermediate recording medium does not aggregate on the surface of the medium, and sublimation of the water-insoluble colorant is not hindered when sublimation transfer is performed. As such an intermediate recording medium, it can be appropriately selected from the following intermediate recording media: "paper-board-and-pulp term [ JIS P0001: 1998 (confirmation in 2008, revised 3/20/1998, issued by the institute of financial and financial institutions on the basis of Japan) on pages 28 to 47, 3 classification f) paper/board varieties and processed products (Nos. 6001 to 6284). Wherein the paper does not include "oil resistance" of No. 6235, "6263" trough (flute), segment, "6273" pulp molding, "6276" carbon paper, "6277" carbon paper for multiple copies, "6278" carbon foam paper for back surface "); and cellophane (hereinafter, "paper and cardboard types and processed products", and cellophane "is referred to as" paper and the like "). Any of these papers and the like can be used as the intermediate recording medium as long as it can be used for sublimation transfer. In the sublimation transfer, as described above, since the heat treatment is usually performed at about 190 to 210 ℃, the intermediate recording medium is preferably stable during the heat treatment.

Examples

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, "part" and "%" are parts by mass and% by mass, respectively, unless otherwise specified.

[ preparation example 1: preparation of dispersant 1

Joncryl 678 (manufactured by BASF Co.) (25 parts), a 48% aqueous sodium hydroxide solution (8.0 parts), ion-exchanged water (71.8 parts), Proxel GXL (manufactured by Lonza Co.) (0.1 part), and Surfynol 104 (manufactured by Air Products Japan) (0.1 part) were mixed as a polymer dispersant, and the mixture was heated to 80 to 90 ℃ and stirred for 10 hours, thereby obtaining a 25% aqueous solution of Joncryl 678 (dispersant 1).

[ preparation example 2: preparation of dispersant 2

Joncryl 690 (manufactured by BASF Co.) (25 parts), a 48% aqueous sodium hydroxide solution (9.0 parts), ion-exchanged water (71.8 parts), Proxel GXL (manufactured by Lonza Co.) (0.1 part), and Surfynol 104 (manufactured by Air Products Japan K.K.) (0.1 part) were mixed as a polymer dispersant, and the mixture was heated to 80 to 90 ℃ and stirred for 10 hours to obtain a 25% aqueous solution of Joncryl 690 (dispersant 2).

[ preparation example 3: preparation of dispersant 3

A mixture of LAVELIN W40 (40% aqueous solution of sodium naphthalenesulfonate formalin condensate, manufactured by first industrial pharmaceutical co., ltd.) (45 parts) as an anionic dispersant, NIKKOL BPS-30 (EO (30 mol) adduct of phytosterol, manufactured by heliochemical co., ltd.) (2 parts), sodium alginate (manufactured by genuine chemical co., ltd.) (0.15 parts), and ion-exchanged water (23 parts) as a nonionic dispersant was dispersed for about 15 hours by a sand mill using glass beads having a diameter of 0.2 mm. Calcium lactate (0.83 part) was added to the obtained liquid, and the mixture was filtered through a glass fiber filter GC-50 (manufactured by toyoyo filter co., ltd.) to remove coarse particles, thereby obtaining an aqueous dispersion.

[ preparation example 4: preparation of 4% sodium alginate aqueous solution

A mixture of sodium alginate (manufactured by pure chemical Co., Ltd.) (4 parts), Proxel GXL (manufactured by Lonza Co., Ltd.) (0.1 part), and ion-exchanged water (95.9 parts) was stirred at room temperature to obtain a 4% sodium alginate aqueous solution.

[ preparation example 5: preparation of 4% SKAT-ULV aqueous solution

A mixture of SKAT-ULV (manufactured by Kimica corporation) (4 parts), Proxel GXL (manufactured by Lonza) (0.1 part), and ion-exchanged water (95.9 parts) was stirred at room temperature to obtain a 4% SKAT-ULV aqueous solution.

[ preparation example 6: preparation of 4% kappa-Carrageenan aqueous solution

A mixture of kappa-carrageenan (manufactured by tokyo chemical industry co., ltd.) (4 parts), Proxel GXL (manufactured by Lonza corporation) (0.1 part), and ion-exchanged water (95.9 parts) was stirred at room temperature to obtain a 4% kappa-carrageenan aqueous solution.

[ preparation example 7: preparation of 4% Cellogen WS-A aqueous solution

A mixture of Cellogen WS-A (manufactured by first Industrial pharmaceutical Co., Ltd.) (4 parts), Proxel GXL (manufactured by LonzA) (0.1 part), and ion-exchanged water (95.9 parts) was stirred at room temperature to obtain A4% Cellogen WS-A aqueous solution.

[ examples 1 to 21: preparation of Dispersion 1 to 21

Glass beads having a diameter of 0.2mm were added to a mixed solution in which the components described in tables 1 to 3 (excluding the polyvalent metal salt) were mixed, and dispersion treatment was performed for about 15 hours under water cooling by a sand mill. After the dispersion treatment, a 4% calcium lactate aqueous solution or a 30% calcium chloride aqueous solution was added to conduct the dispersion treatment for about 2 hours. Next, the obtained dispersion was filtered through a glass fiber filter paper GC-50 (manufactured by Toyo Filter paper Co., Ltd., pore diameter of filter: 0.5 μm) to remove components having large particle sizes, thereby obtaining dispersions 1 to 21.

Comparative examples 1 to 11: preparation of Dispersion 22 to 32

Glass beads having a diameter of 0.2mm were added to a mixed solution in which the components described in tables 4 to 5 were mixed, and dispersion treatment was performed for about 15 hours under water cooling conditions using a sand mill. The obtained dispersion was filtered through a glass fiber filter paper GC-50 (manufactured by Toyo Filter paper Co., Ltd., pore diameter of filter: 0.5 μm) to remove components having large particle sizes, thereby obtaining dispersions 22 to 32.

Abbreviations and the like in tables 1 to 5 have the following meanings.

DR 60: c.i. disperse red 60

DY 54: c.i. disperse yellow 54

DOr 25: c.i. disperse orange 25

DOr 60: c.i. disperse orange 60

DB 56: c.i. disperse blue 56

DB 359: c.i. disperse blue 359

DB 360: c.i. disperse blue 360

DR 364: c.i. disperse red 364

DY 232: c.i. disperse yellow 232

VANILLEX N: lignosulfonic acid (manufactured by Japan paper-making Co., Ltd.)

LAVELIN W40: sodium naphthalenesulfonate formalin condensate (first Industrial pharmaceutical Co., Ltd.)

BPS-30: NIKKOL BPS-30 (manufactured by Nikkol chemical Co., Ltd.)

Surfynol 104: acetylene glycol surfactant (Air Products Japan K.K.)

Proxel GXL (S) (manufactured by Lonza corporation)

Sodium alginate (pure chemical company)

SKAT-ULV: sodium alginate (Kimica, Kyoho)

Kappa-carrageenan (manufactured by Tokyo chemical industry Co., Ltd.)

Cellogen WS-A: sodium carboxymethylcellulose (first Industrial pharmaceutical Co., Ltd.)

Calcium lactate (pure chemical company)

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

[ evaluation of Dispersion ]

The dispersion liquid 1 to 32 obtained as described above were evaluated for the initial particle size of the dispersion liquid, the particle size of the dispersion liquid with time, and the storage stability of the dispersion liquid by the following evaluation methods. The results are shown in tables 1 to 5.

(initial particle diameter of dispersion)

The dispersions 1 to 32 of examples and comparative examples were diluted 1000-fold with water, and the volume average particle diameter (D50) was measured using Microtrac UPA (manufactured by nippon corporation), and the value thereof was defined as the initial particle diameter of the dispersion. The evaluation criteria are as follows. The level below grade 2 is a level not withstanding actual use.

Evaluation criteria-

Grade 5: the primary particle size of the dispersion is less than 100 nm.

Grade 4: the primary particle size of the dispersion is 100nm or more and less than 120 nm.

Grade 3: the primary particle diameter of the dispersion is 120nm or more and less than 150 nm.

Grade 2: the primary particle size of the dispersion is 150nm or more and less than 180 nm.

Grade 1: the primary particle size of the dispersion is 180nm or more.

(particle diameter of dispersion with time)

The dispersions 1 to 32 (100 g each) of examples and comparative examples were sealed in a glass bottle and left at 60 ℃ for 14 days. The dispersion after standing was diluted 1000-fold with water, and the volume average particle diameter (D50) was measured using Microtrac UPA (manufactured by japan electronics corporation), and the value thereof was defined as the particle diameter of the dispersion with time. The evaluation criteria are as follows. The level below grade 2 is a level not withstanding actual use.

Evaluation criteria-

Grade 5: the particle size of the dispersion liquid is less than 100 nm.

Grade 4: the particle diameter of the dispersion liquid is more than 100nm and less than 120 nm.

Grade 3: the particle diameter of the dispersion liquid is more than 120nm and less than 150 nm.

Grade 2: the particle diameter of the dispersion liquid is more than 150nm and less than 180 nm.

Grade 1: the particle diameter of the dispersion liquid is more than 180 nm.

(storage stability of dispersion)

Water was added to the dispersions 1 to 32 of examples and comparative examples to dilute the dispersion to 10000 times, and absorbance at the maximum absorption wavelength of 400 to 780nm was measured. Further, the dispersions 1 to 32 (100 g each) were sealed in a glass bottle and left at 60 ℃ for 14 days. The dispersion after standing was diluted 10000 times with water, and absorbance at the maximum absorption wavelength was measured in the same manner. The absorbance before leaving the reaction mixture was set to 100%, and the absorbance after leaving the reaction mixture was calculated and used to evaluate the storage stability of the dispersion. The evaluation criteria are as follows. The level below grade 2 is a level not withstanding actual use.

Evaluation criteria-

Grade 5: the absorbance after standing was 95% or more.

Grade 4: the absorbance after standing was 90% or more and less than 95%.

Grade 3: the absorbance after standing is 80% or more and less than 90%.

Grade 2: the absorbance after standing is 60% or more and less than 80%.

Grade 1: the absorbance after standing was less than 60%.

From the results shown in tables 1 to 5, it is clear that the dispersions 1 to 21 of the examples are excellent in particle size stability with time and storage stability.

[ examples 22 to 42: preparation of inks 1 to 21

Each of the components shown in tables 6 to 8 below was mixed and stirred for 30 minutes, and then filtered by a glass fiber filter GC-50 (manufactured by Toyo Filter paper Co., Ltd.) to obtain inks 1 to 21 each having a dye content of 5%.

Comparative examples 12 to 22: preparation of inks 22 to 32

Inks 22 to 32 each having a dye content of 5% were prepared by mixing and stirring the components described in tables 9 to 10 for 30 minutes, and then filtering the mixture with a glass fiber filter paper GC-50 (manufactured by Toyo Filter paper Co., Ltd.).

Abbreviations and the like in tables 6 to 10 have the following meanings.

BYK 348: polyether modified polydimethylsiloxane (BYK Chemie Co., Ltd.)

Gly: glycerol

TEGMME: triethylene glycol monomethyl ether

[ Table 6]

[ Table 7]

[ Table 8]

[ Table 9]

[ Table 10]

[ evaluation of ink ]

The inks 1 to 32 obtained as described above were evaluated for ink storage stability by the following evaluation method. The results are shown in tables 6 to 10.

(storage stability of ink)

Water was added to the inks 1 to 32 of examples and comparative examples to dilute the mixture to 10000 times, and absorbance at a maximum absorption wavelength of 400 to 780nm was measured. Further, 1 to 32 g (100 g each) of the inks were sealed in a glass bottle and left at 60 ℃ for 14 days. Water was added to the inks 1 to 32 after the standing to dilute the mixture to 10000 times, and the absorbance at the maximum absorption wavelength was measured in the same manner. The absorbance before leaving was set to 100%, and the absorbance after leaving was calculated and used to evaluate the storage stability of the ink. The evaluation criteria are as follows. The level below grade 2 is a level not withstanding actual use.

Evaluation criteria-

Grade 5: the absorbance after standing was 95% or more.

Grade 4: the absorbance after standing was 90% or more and less than 95%.

Grade 3: the absorbance after standing is 80% or more and less than 90%.

Grade 2: the absorbance after standing is 60% or more and less than 80%.

Grade 1: the absorbance after standing was less than 60%.

As is clear from the results in tables 6 to 10, the inks 1 to 21 of the examples are excellent in storage stability.

[ preparation of dyed Fabric ]

Solid patterns were printed on transfer paper as an intermediate recording medium using inks 1 to 21 of the examples shown in tables 6 to 8 by an inkjet printer (PX-105, manufactured by seiko Epson corporation). The printed transfer paper was cut to 35cm × 40 cm. The ink-adhering surface of the cut transfer paper was laminated with polyester cloth (Pongee fabric, Pongee) having the same size, and then heat-treated at 200 ℃ for 60 seconds using a transfer machine (TP-600 a2, manufactured by seiko corporation) to sublimation-transfer-dye the polyester cloth from the transfer paper. As a result, desired colors can be obtained.