JP2018030943A - Non-white inkjet printing ink composition and inkjet printing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-white inkjet printing ink composition that improves the coloring of a resultant image and also inhibits the uneven flocculation for the improved image quality, thereby giving an image having excellent washing fastness, and an inkjet printing method.SOLUTION: A non-white inkjet printing ink composition is used by attached to a fabric with a reaction liquid for flocculating components of the ink composition. The inkjet printing ink composition has: a non-white pigment dispersion that is not flocculated with the reaction liquid; a resin dispersion that is flocculated with the reaction liquid; and water.SELECTED DRAWING: None

Description

  The present invention relates to a non-white inkjet printing ink composition and an inkjet printing method.

  Printing methods for recording images on fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics are known. In recent years, an ink composition used for printing (hereinafter also referred to as “ink”) can be used efficiently. Therefore, the use of an ink jet recording method has been studied. In an ink jet textile printing method using this ink jet recording method, ink droplets are ejected from a nozzle of a head and adhered to the fabric, thereby forming an image of the ink coating on the fabric.

  The ink used in such an ink jet textile printing method includes, for example, a color material such as a pigment or a dye, a dispersant (surfactant), a solvent (water, an organic solvent, or the like). Here, pigment printing using a pigment as a color material is known because it tends to be superior in characteristics such as light resistance of a recorded image rather than using a dye as a color material. In this pigment printing, inkjet printing using a reaction liquid containing an aggregating agent that aggregates with an ink component has been studied for the purpose of improving the color developability and washing fastness of the obtained image (for example, Patent Document 1). .

JP 2011-17330 A

  In a non-white pigment printing, when a reaction liquid is used to improve color developability, it is possible to prevent the ink from penetrating into the fabric and improve the color (density) of the recorded matter. However, since the reaction liquid reacts with the pigment in the ink, the obtained image is likely to have uneven aggregation and the image quality may be inferior. Further, since the penetration of the pigment into the fabric is suppressed, the fastness of the recorded matter tends to be inferior. For this reason, in non-white pigment printing using a reaction solution, it is difficult to obtain an ink composition that is excellent in color development, suppresses uneven aggregation, improves image quality, and provides an image with excellent fastness.

  Therefore, some aspects according to the present invention solve at least a part of the above-described problems, thereby improving the image quality by suppressing aggregation unevenness while improving the color development of the obtained image, thereby improving the fastness to washing. The present invention provides a non-white ink jet printing ink composition and an ink jet printing method capable of obtaining an excellent image.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the non-white inkjet printing ink composition according to the present invention is:
An ink-jet printing ink composition used by adhering to a fabric together with a reaction liquid for aggregating the components of the ink composition,
It contains a non-white pigment dispersion that does not aggregate with the reaction liquid, a resin dispersion that aggregates with the reaction liquid, and water.

  According to the non-white inkjet printing ink composition of Application Example 1, since the reaction liquid reacts with the resin dispersion instead of the non-white pigment dispersion in the ink, aggregation unevenness is improved while improving the color development of the obtained image. It is possible to provide a non-white ink-jet printing ink composition which can improve the image quality by suppressing the above and obtain an image excellent in washing fastness.

[Application Example 2]
In the above application example,
The non-white inkjet textile printing ink composition may be used by being attached to the fabric with a maximum adhesion amount of 20 mg / inch ² or less.

  According to Application Example 2, when the adhesion amount is in the above range, the color of the obtained image is improved, the aggregation unevenness is suppressed, the image quality is improved, and an image excellent in washing fastness can be obtained.

[Application Example 3]
In the above application example,
The non-white pigment dispersion may be obtained by dispersing a pigment with at least one of a non-resin dispersant and a nonionic resin dispersant.

  According to Application Example 3, the non-white pigment dispersion is sufficiently dispersed, the color development of the obtained image is improved, the aggregation unevenness is suppressed, the image quality is improved, and an image excellent in washing fastness can be obtained. .

[Application Example 4]
In the above application example,
The nonionic resin dispersant can be used.

  According to the application example 4, the color development of the obtained image is further improved.

[Application Example 5]
In the above application example,
The resin dispersion may be a self-dispersing resin dispersion.

  According to Application Example 5, even with a self-dispersing pigment that tends to aggregate, the aggregation unevenness is suppressed, the image quality is improved, and an image excellent in washing fastness can be obtained.

[Application Example 6]
In the above application example,
The content of the non-white pigment dispersion may be 1% by mass or more and 7% by mass or less, and the content of the resin dispersion may be 1% by mass or more and 15% by mass or less.

  According to Application Example 6, the non-white pigment dispersion is sufficiently dispersed, the color development of the obtained image is improved, the aggregation unevenness is suppressed, the image quality is improved, and an image excellent in washing fastness can be obtained. .

[Application Example 7]
In the above application example,
The reaction solution may contain at least one of a polyvalent metal salt, an organic acid, and a cationic resin as a flocculant.

  According to Application Example 7, by including the aggregating agent, the color of the obtained image is improved, the aggregation unevenness is suppressed, the image quality is improved, and an image excellent in washing fastness can be obtained.

[Application Example 8]
One aspect of the inkjet textile printing method according to the present invention is as follows:
A non-white inkjet printing ink composition comprising a step of attaching a reaction liquid to a fabric, a non-white pigment dispersion that does not aggregate with the reaction liquid, a resin dispersion that aggregates with the reaction liquid, and water. And a step of adhering to a fabric.

  According to Application Example 8, since the reaction liquid reacts with the resin dispersion instead of the non-white pigment dispersion in the ink by performing the ink jet printing method described in the above application example, color development of the obtained image It is possible to provide an ink jet textile printing method that improves image quality by suppressing aggregation unevenness while improving the image quality, and can provide an image having excellent washing fastness.

[Application Example 9]
Furthermore, the process of attaching the white inkjet textile printing ink composition containing a white pigment to a fabric by the inkjet method can be provided.

  According to Application Example 9, even when a step of attaching the white inkjet textile printing ink composition to the fabric is provided, the image quality is improved by suppressing aggregation unevenness while improving the color of the obtained image, thereby improving the fastness to washing. It is possible to provide an ink-jet printing method capable of obtaining an excellent image.

[Application Example 10]
The maximum adhesion amount of the non-white inkjet printing ink composition may be 30 mg / inch ² or less, and the maximum adhesion amount of the white inkjet printing ink composition may be 50 mg / inch ² or more.

  According to the application example 10, when the maximum adhesion amount of the white ink composition is as described above, the white color developability is good, and the color development particularly when adhering to a dark cloth is excellent, and the inkjet printing method is preferable as a background image. Can be provided. In addition, when the adhesion amount is in the above range, the fastness of the image becomes excellent, and an ink jet printing method in which the aggregation unevenness is not conspicuous can be provided.

  Several embodiments of the present invention will be described below. Embodiment described below demonstrates an example of this invention. The present invention is not limited to the following embodiments, and includes various modifications that are implemented without departing from the scope of the present invention. Note that not all of the configurations described below are essential configurations of the present invention.

1. Inkjet printing method The inkjet printing method according to the present embodiment includes a step of attaching a reaction liquid to a fabric, a non-white pigment dispersion that does not aggregate with the reaction liquid, a resin dispersion that aggregates with the reaction liquid, water, And a step of adhering a non-white ink-jet printing ink composition containing the composition to a fabric by an ink-jet method. Hereinafter, the inkjet printing method according to the present embodiment will be described in the order of the fabric, the reaction liquid, the non-white inkjet printing ink composition, the white inkjet printing ink composition, and the inkjet printing method.

1.1. Fabric The inkjet printing method according to the present embodiment is performed using a fabric. The material constituting the fabric is not particularly limited. For example, natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane; and biodegradable materials such as polylactic acid. Examples thereof include fibers, and these blended fibers may be used. As the fabric, the above-described fibers may be in any form such as a woven fabric, a knitted fabric, and a non-woven fabric. Among these, the fabric used in the present embodiment is more preferably formed of fibers containing cellulose such as cotton and hemp. By using such a fabric, better fixability of the pigment can be obtained.

  The fabric weight used in this embodiment is 1.0 oz (ounces) to 10.0 oz, preferably 2.0 oz to 9.0 oz, more preferably 3.0 oz to 8.0 oz, and even more preferably. Is in the range of 4.0 oz to 7.0 oz. In the inkjet textile printing method of the present embodiment, since the reaction liquid described later is used, the flocculant in the reaction liquid can be appropriately disposed when the reaction liquid is applied to the fabric having a basis weight in such a range. Therefore, good pigment printing can be realized. In other words, if the fabric weight is within such a range, the reaction solution can be sufficiently applied, and good printing can be performed by the inkjet printing method of the present embodiment. Furthermore, since the inkjet printing method of the present embodiment uses a reaction solution, it can be applied to a plurality of types of fabrics having different weights, and good printing can be performed.

1.2. Reaction liquid The reaction liquid used in the present embodiment aggregates the components of the ink composition, and is used in an ink jet printing method in which a non-white ink jet printing ink composition described later is attached to a fabric by an ink jet method. More specifically, the reaction liquid according to the present embodiment is attached to the cloth, and then the non-white ink jet printing ink composition is attached to the cloth by an ink jet method to be used for textile printing.

1.2.1. Flocculant The reaction liquid used in the present embodiment is, for example, a polyvalent metal salt, an organic acid, a cationic compound (cationic resin, cationic) as a flocculant for aggregating the components of the non-white inkjet printing ink composition described below. Surfactants, etc.). These flocculants may be used alone or in combination of two or more.

  These aggregating agents are for aggregating the resin dispersion without aggregating the non-white pigment dispersion among the components of the printing ink composition described below. That is, these aggregating agents have a function of aggregating the resin dispersion by interacting with at least a part of the components of the resin dispersion contained in the textile printing ink composition. Thereby, it is possible to improve the color developability and fixability of an image recorded by the textile printing ink composition. Further, the flocculant can increase the viscosity (thickening) of the textile printing ink composition by interacting with at least a part of the resin dispersion contained in the textile printing ink composition. Thereby, it can suppress that a textile-printing ink composition permeate | penetrates the inside of a fabric too much, and can improve color developability. Further, there are cases where bleeding and bleeding can be reduced by increasing the viscosity of the textile printing ink composition.

<Multivalent metal salt>
The polyvalent metal salt is a compound that is composed of divalent or higher polyvalent metal ions and anions that bind to these polyvalent metal ions and is soluble in water. Specific examples of the polyvalent metal ions include divalent metal ions such as Ca ²⁺ , Cu ²⁺ , Ni ²⁺ , Mg ²⁺ , Zn ²⁺ and Ba ²⁺ ; trivalent metal ions such as Al ³⁺ , Fe ³⁺ and Cr ^3+. It is done. Examples of the anion include Cl ⁻ , I ⁻ , Br ⁻ , SO 4 ²⁻ , ClO ³⁻ , NO ³⁻ , HCOO ⁻ , and CH ₃ COO ⁻ .

As these polyvalent metal salts, carboxylate (formic acid, acetic acid, benzoate, etc.), sulfate, nitrate, chloride, and thiocyanate are suitable. Among them, preferably, calcium salt or magnesium salt of carboxylic acid (formic acid, acetic acid, benzoate, etc.), calcium salt or magnesium salt of sulfuric acid, calcium salt or magnesium salt of nitric acid, calcium chloride, magnesium chloride, and thiocyanic acid. A calcium salt or a magnesium salt is mentioned. In addition, a polyvalent metal salt may be used individually by 1 type, and may use 2 or more types together. Among these polyvalent metal salts, calcium salts and magnesium salts are preferable from the viewpoint of the stability of the reaction solution and the reactivity as a flocculant.

<Organic acid>
Examples of organic acids include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, and tartaric acid. , Lactic acid, sulfonic acid, orthophosphoric acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, or derivatives of these compounds, or salts thereof Etc. are preferable. An organic acid may be used individually by 1 type, and may use 2 or more types together.

<Cationic compound>
Although it does not specifically limit as a cationic compound, For example, a cationic resin, a cationic surfactant, etc. are mentioned. The cationic compound neutralizes the surface charge of the components contained in the printing ink composition or changes the pH of the printing ink composition to cause the components to aggregate or precipitate, thereby aggregating or thickening the printing ink composition. . Examples of the component that reacts with the cationic organic compound contained in the textile printing ink composition include resins described later.

  Examples of organic acid salts include polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, lactic acid, sulfonic acid, and orthophosphoric acid. And salts of pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid and the like. The counter ion (cation) of the organic acid salt is not particularly limited, and examples thereof include ions of sodium, potassium, calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, iron and the like. An organic acid salt may be used individually by 1 type, and may use 2 or more types together.

  Examples of the cationic resin include a cationic urethane resin, a cationic olefin resin, and a cationic allylamine resin.

  As the cationic urethane resin, known ones can be appropriately selected and used. Examples of the cationic urethane-based resin include hydran CP-7010, CP-7020, CP-7030, CP-7040, CP-7050, CP-7060, CP-7610 (trade name, Dainippon Ink and Chemicals, Inc. Manufactured), Superflex 600, 610, 620, 630, 640, 650 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), urethane emulsion WBR-2120C, WBR-2122C (trade name, manufactured by Taisei Fine Chemical Co., Ltd.), etc. Can be used.

  The cationic olefin resin has an olefin such as ethylene or propylene in the structural skeleton, and a known one can be appropriately selected and used. The cationic olefin resin may be in an emulsion state dispersed in a solvent containing water, an organic solvent, or the like. As the cationic olefin resin, commercially available products can be used, and examples thereof include Arrow Base CB-1200, CD-1200 (trade name, manufactured by Unitika Ltd.) and the like.

  As the cationic allylamine resin, known resins can be appropriately selected and used. For example, polyallylamine hydrochloride, polyallylamine amide sulfate, allylamine hydrochloride / diallylamine hydrochloride copolymer, allylamine acetate / diallylamine acetic acid Salt copolymer, allylamine acetate / diallylamine acetate copolymer, allylamine hydrochloride / dimethylallylamine hydrochloride copolymer, allylamine / dimethylallylamine copolymer, polydiallylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldiallylamine amide sulfate, polymethyldiallylamine acetic acid Salt, polydiallyldimethylammonium chloride, diallylamine acetate / sulfur dioxide copolymer, diallylmethylethylammonium ethyl sulfate - sulfur dioxide copolymers, methyl diallyl amine hydrochloride-sulfur dioxide copolymers, diallyldimethylammonium chloride-sulfur dioxide copolymers, diallyldimethylammonium chloride-acrylamide copolymer and the like.

  As such a cationic allylamine resin, commercially available products can be used. For example, PAA-HCL-01, PAA-HCL-03, PAA-HCL-05, PAA-HCL-3L, PAA-HCL- 10L, PAA-H-HCL, PAA-SA, PAA-01, PAA-03, PAA-05, PAA-08, PAA-15, PAA-15C, PAA-25, PAA-H-10C, PAA-D11- HCL, PAA-D41-HCL, PAA-D19-HCL, PAS-21CL, PAS-M-1L, PAS-M-1, PAS-22SA, PAS-M-1A, PAS-H-1L, PAS-H- 5L, PAS-H-10L, PAS-92, PAS-92A, PAS-J-81L, PAS-J-81 (trade name, Nittobo Medical Association Etsu Chemical Co., Ltd.), Haimo Neo-600, Haimorokku Q-101, Q-311, Q-501, high-Max SC-505, SC-505 (trade name, can be used Haimo Co., Ltd.), and the like.

  Examples of the cationic surfactant include primary, secondary and tertiary amine salt type compounds, alkylamine salts, dialkylamine salts, aliphatic amine salts, fatty acid amidoamines, benzalkonium salts, quaternary salts. Ammonium salts, quaternary alkyl ammonium salts, alkyl pyridinium salts, sulfonium salts, phosphonium salts, onium salts, imidazolinium salts, alkyl betaines, fatty acid amide betaines, alkyl amine oxides and the like can be mentioned. Specifically, alkyltrimethylammonium salts, dialkyldimethylammonium salts and alkyldimethylbenzylammonium salts are exemplified as quaternary ammonium series, and N-methylbishydroxyethylamine fatty acid ester hydrochloride is exemplified as amine salt series. Further, for example, lauryl Amine, palmamine, rosinamine and other hydrochlorides, acetates, lauryltrimethylammonium chloride, cetyltributylammonium chloride, benzyltributylammonium chloride, benzalkonium chloride, dimethylethyllaurylammonium ethylsulfate, dimethylethyloctylammonium ethylsulfate, Trimethyllauryl ammonium hydrochloride, cetylpyridinium chloride, cetylpyridinium bromide, dihydroxyethyl Uriruamin, decyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl ammonium chloride, hexadecyl dimethyl ammonium chloride, octadecyl dimethyl ammonium chloride, and the like.

  As such a cationic surfactant, commercially available products can be used. For example, cationogen TML, cationogen TMP, cationogen TMS, cationogen ES-O, cationogen ES-L, cationogen ES-L-9, cationogen ES -P (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Amorgen S-H, Amorgen K, Amorgen CB-H, Amorgen HB-C, Amorgen AOL (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

  The concentration of the flocculant may be 0.03 mol / kg or more in 1 kg of the reaction solution. Moreover, in 1 kg of reaction liquid, 0.1 mol / kg or more and 1.5 mol / kg or less may be sufficient, and 0.2 mol / kg or more and 0.9 mol / kg or less may be sufficient. The content of the flocculant may be, for example, 0.1% by mass or more and 10% by mass or less, or 0.5% by mass or more and 8.0% by mass or less with respect to the total mass of the reaction solution. It may be 1.0 mass% or more and 5.0 mass% or less.

  The confirmation that the aggregating agent reacts with the resin contained in the ink composition can be performed by, for example, whether or not the resin agglomerates in the “resin aggregability test”. The “resin cohesiveness test” is performed by, for example, visually stirring whether or not a precipitate is generated in the mixed solution by mixing and stirring the coagulant solution adjusted to a predetermined concentration in a resin solution containing the resin at a predetermined concentration. Do this by checking.

1.2.2. Other ingredients <Water>
The reaction liquid according to this embodiment may contain water. Examples of water include water from which ionic impurities have been removed as much as possible, such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and ultrapure water. In addition, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of bacteria and fungi can be prevented when the reaction solution is stored for a long time.

  The water content is 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, based on the total amount of the reaction solution. The water in the reaction liquid includes, for example, a resin particle dispersion used as a raw material and water to be added. In this embodiment, when the content of water in the reaction solution is 40% by mass or more, the reaction solution can have a relatively low viscosity. Further, the upper limit of the water content is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less with respect to the total amount of the reaction solution.

<Water-soluble organic solvent>
In this embodiment, the reaction liquid may contain a water-soluble organic solvent. In some cases, the water-soluble organic solvent can improve the wettability of the reaction liquid with respect to the recording medium. Examples of the water-soluble organic solvent include at least one of esters, alkylene glycol ethers, cyclic esters, and alkoxyalkylamides. Moreover, as a water-soluble organic solvent, nitrogen-containing compounds other than these, saccharides, amines, etc. may be sufficient. Further, the reaction liquid may contain a water-soluble organic solvent that can be used in the textile printing ink composition described later.

  Further, the reaction solution may contain 1,2-alkanediol. When the reaction solution contains 1,2-alkanediol, the permeability of the reaction solution to the fabric (to be printed) can be made moderate. 1,2-alkanediol is a compound having a structure in which two hydroxyl groups (hydroxyl groups) are bonded to the 1st and 2nd carbons of one terminal of an alkane (hydrocarbon) having 3 or more carbon atoms. It is.

  1,2-alkanediol has a hydrophobic part composed of a hydrocarbon chain and a hydrophilic part formed by arranging two hydroxyl groups at the end of the hydrocarbon chain. The hydrocarbon chain may be linear or branched, but in the present embodiment, one in which two hydroxyl groups are arranged at the end of the linear hydrocarbon is preferable.

Examples of such 1,2-alkanediol include 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2 -Carbon number of octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, 1,2-tridecanediol, 1,2-tetradecanediol, etc. The 1,2-alkanediol of 3 or more and 14 or less is mentioned. Among these, in this embodiment, from the viewpoint that the reaction solution does not excessively reduce the permeability to the fabric and the interfacial tension, the number of carbon atoms of 1,2-alkanediol is preferably 4 or more and 12 or less. It is preferably 4 or more and 10 or less, more preferably 4 or more and 9 or less, and particularly preferably 6 or more and 9 or less.

  Further, the reaction solution may contain a plurality of the above-exemplified 1,2-alkanediols. The total content of 1,2-alkanediol with respect to the entire reaction solution is preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, and even more preferably 0.5%. The mass is 10% by mass or more.

<Resin emulsion>
In the present embodiment, the reaction solution may contain a resin emulsion. By containing the resin emulsion, the fixing (fixing) property of the pigment contained in the ink composition to the fabric may be further improved. Further, the resin emulsion may function as a sealing agent that suppresses penetration of the reaction liquid and / or the ink composition into the fabric.

  Examples of such resin emulsions include, but are not limited to, at least one resin emulsion selected from urethane, styrene / acrylic, acrylic, and vinyl chloride-vinyl acetate. In the reaction solution, one or more of these resin emulsions can be used.

  The urethane resin emulsion is not particularly limited as long as it has a urethane bond in the molecule, but in addition to the urethane bond, a polyether type urethane resin emulsion containing an ether bond in the main chain, an ester bond in the main chain. Polyester-type urethane resin emulsions including polycarbonate-type urethane resin emulsions including a carbonate bond in the main chain can also be used.

  The D50 of the resin particles in the resin emulsion is preferably 30 nm or more and 300 nm or less, and more preferably 40 nm or more and 100 nm or less. When D50 is within the above range, the resin emulsion particles can be uniformly dispersed in the reaction solution. In addition, the rub resistance of the printed matter is further improved.

As commercial products of these resin emulsions, Microgel E-1002, E-5002 (trade name, styrene-acrylic resin emulsion manufactured by Nippon Paint Co., Ltd.), Boncoat 4001 (trade name, manufactured by DIC, acrylic resin emulsion), Boncoat 5454 (trade name, styrene-acrylic resin emulsion manufactured by DIC), Polysol AM-710, AM-920, AM-2300, AP-4735, AT-860, PSASE-4210E (acrylic resin emulsion), Polysol AP- 7020 (styrene / acrylic resin emulsion), Polysol SH-502 (vinyl acetate resin emulsion), Polysol AD-13, AD-2, AD-10, AD-96, AD-17, AD-70 (ethylene / vinyl acetate resin) Emulsion) Polysol PSASE-6010 (ethylene / vinyl acetate resin emulsion) (trade name, manufactured by Showa Denko KK), Polysol SAE1014 (trade name, styrene-acrylic resin emulsion, manufactured by Nippon Zeon), Cybinol SK-200 (trade name, acrylic) Resin emulsion, manufactured by Seiden Chemical Co., Ltd.), AE-120A (trade name, manufactured by JSR, acrylic resin emulsion), AE373D (trade name, manufactured by Etec, carboxy-modified styrene / acrylic resin emulsion), Seikadyne 1900W (manufactured by Dainichi Seika Kogyo Co., Ltd.) Trade name, ethylene / vinyl acetate resin emulsion), Viniblanc 2682 (acrylic resin emulsion), Vinibrand 2886 (vinyl acetate / acrylic resin emulsion), Vinibrand 5202 (acrylic acid acrylic resin emulsion) ( (Trade name, manufactured by Shin Chemical Industry Co., Ltd.), Elitel KA-5071S, KT-8803, KT-9204, KT-8701, KT-8904, KT-0507 (trade name, manufactured by Unitika Ltd., polyester resin emulsion), Hitech SN-2002 ( Toho Chemical Co., Ltd. product name, polyester resin emulsion), Takelac W-6020, W-635, W-6061, W-605, W-635, W-6021 (Mitsui Chemicals Polyurethane product name, urethane resin emulsion) , Superflex 870, 800, 150, 420, 460, 470, 610, 700 (trade name, urethane resin emulsion manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Permarin UA-150 (manufactured by Sanyo Chemical Industries, Ltd., urethane resin emulsion) ), Sancure 2710 (Nippon Lubrizol) Urethane resin emulsion), NeoRez R-9660, R-9737, R-940 (Enomoto Kasei Co., urethane resin emulsion), Adekabon titer HUX-380, 290K (ADEKA Co., urethane system) Resin emulsion), Mobile 966A, Mobile 7320 (manufactured by Nippon Synthetic Chemical Co., Ltd.), Jonkrill 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, 7610 (above, manufactured by BASF), NK binder R-5HN (Shin Nakamura Chemical Co., Ltd.) Made by company , HYDRAN WLS-210 (non-crosslinked polyurethane: DIC Co., Ltd.), and the like.

  When the resin emulsion is contained in the reaction solution, the content of the resin emulsion in the reaction solution in terms of solid content is preferably 1 to 20% by mass when the total mass of the reaction solution is 100% by mass, More preferably, it is 1.5-15 mass%, More preferably, it is 2-10 mass%. When the content of the resin emulsion in terms of solid content is within the above range, the washing durability of the image is further improved. The amount in terms of solid content refers to the amount excluding substances other than the resin (solid content) in the resin emulsion.

  In addition, when a resin emulsion is contained in the reaction liquid and the resin emulsion is blended in the ink composition, both resin emulsions may be the same or different.

<Surfactant>
In the present embodiment, the reaction solution may contain a surfactant. The surfactant may be any of nonionic surfactants, anionic surfactants, and amphoteric surfactants, whether or not the above cationic surfactants are employed. You may use together. The surfactant can reduce the interfacial tension of the reaction solution and increase the permeability to the fabric.

  When a surfactant is added to the reaction solution, the total amount of the surfactant is less than 0.5% by weight, preferably less than 0.1% by weight, more preferably 0.05% by weight, based on the entire reaction solution. Less than, particularly preferably less than 0.01% by mass. In the reaction solution, the surfactant is an optional component, and even if it is not contained, the function and action of the reaction solution can be sufficiently exerted.

  As the nonionic surfactant, at least one of acetylene glycol surfactant, acetylene alcohol surfactant, fluorosurfactant, and polysiloxane surfactant is preferable. When the reaction solution contains these surfactants, the wettability to the fabric and the dispersion stability of the pigment are further improved.

Examples of the acetylene glycol surfactant and the acetylene alcohol surfactant include, but are not limited to, 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7. , 9-tetramethyl-5-decyne-4,7-diol alkylene oxide adduct, and 2,4-dimethyl-5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol, Selected from alkylene oxide adducts of 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3ol, 2,4-dimethyl-5-hexyn-3-ol One or more types can be exemplified. Commercially available acetylene glycol surfactants and acetylene alcohol surfactants can also be used. Surfynol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA (all are trade names, manufactured by Air Products and Chemicals, Inc.), Olphin B, Y, P, A STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100 (all trade names, Kawaken Fine Chemical Co., Ltd.).

  As the fluorosurfactant, commercially available ones may be used, and examples thereof include Megafac F-479 (manufactured by DIC Corporation), BYK-340 (manufactured by Big Chemie Japan), and the like.

  As the polyorganosiloxane-based surfactant, commercially available ones can be used. For example, Olfine PD-501, Olfine PD-502, Olfine PD-570 (all manufactured by Nissin Chemical Industry Co., Ltd.), BYK-347, BYK-348, BYK-302 (all are manufactured by Big Chemie Co., Ltd.) and the like.

  BYK-348 and BYK-302 are both siloxane-based surfactants (silicon-based surfactants), but when blended in a reaction solution, BYK-302 has the ability to lower the interfacial tension. Since it is small, it can be used more suitably.

  Furthermore, examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, alkyl glucoside, polyoxyalkylene glycol alkyl ether, polyoxyalkylene glycol, polyoxyalkylene glycol alkyl phenyl ether, and sucrose fatty acid. Ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene acetylene glycol, polyoxyalkylene glycol alkylamine, polyoxyethylene alkylamine, polyoxyethylene alkylamine oxide, fatty acid alkanolamide, alkyl Roll amide, polyoxyethylene polyoxypropylene block It may also be used polymers, and the like.

  Examples of the anionic surfactant include higher fatty acid salt, soap, α-sulfo fatty acid methyl ester salt, linear alkylbenzene sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, monoalkyl phosphate ester salt, α -Olefin sulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonate, naphthalene sulfonate, alkane sulfonate, polyoxyethylene alkyl ether sulfate, sulfosuccinate, polyoxyalkylene glycol alkyl ether phosphate ester, etc. Is mentioned.

Examples of amphoteric surfactants include alkylamino fatty acid salts as amino acids, alkylcarboxyl betaines as betaines, and alkylamine oxides as amine oxides. The amphoteric surfactant is not limited to these. A plurality of the surfactants may be used in combination.

<Other ingredients>
Various additives, such as a chelating agent, an antiseptic, a pH adjuster, a viscosity adjuster, an antioxidant, and an antifungal agent, can be appropriately added to the reaction solution of this embodiment as necessary.

1.2.3. Method for Preparing Reaction Solution The reaction solution used in the present embodiment can be produced by dispersing and mixing the above components by an appropriate method. For example, after sufficiently stirring each of the above components, the target reaction solution can be obtained by performing filtration to remove coarse particles and foreign matters that cause clogging.

1.2.4. Physical Properties of Reaction Solution In the present embodiment, the reaction solution has a surface tension at 25 ° C. of 30 mN / m or more, preferably 35 mN / m or more, more preferably 38 mN, from the viewpoint of appropriate permeability to the fabric. / M or more, more preferably 40 mN / m or more. The surface tension is measured by using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) by confirming the surface tension when the platinum plate is wetted with the composition in an environment of 25 ° C. can do.

  Further, the reaction solution may be attached to the fabric by an ink jet method, and in that case, the viscosity at 20 ° C. is preferably 1.5 mPa · s to 15 mPa · s, and preferably 1.5 mPa. More preferably, it is s or more and 5 mPa · s or less, and more preferably 1.5 mPa · s or more and 3.6 mPa · s or less.

  On the other hand, the reaction solution may be performed by a method other than the inkjet method. Examples of such methods include non-contact methods such as a method of applying the reaction liquid to the cloth using various sprays, a method of applying the cloth by immersing the cloth in the reaction liquid, and a method of applying the treatment liquid to the cloth with a brush or the like. And any of the contact methods or a combination thereof.

  When the reaction liquid is attached to the fabric by a method other than the ink jet method, the viscosity at 20 ° C. may be higher than that by the ink jet method, for example, 1.5 mPa · s or more and 100 mPa · s or less. Preferably, it is 1.5 mPa · s or more and 50 mPa · s or less, and more preferably 1.5 mPa · s or more and 20 mPa · s or less. The viscosity is measured by using a viscoelasticity tester MCR-300 (manufactured by Pysica), increasing the Shear Rate to 10 to 1000 in an environment of 20 ° C., and reading the viscosity at Shear Rate 200. Can be measured.

1.3. Non-white inkjet printing ink composition The non-white inkjet printing ink composition according to this embodiment is an inkjet printing ink composition that is used by adhering to a fabric together with a reaction liquid that aggregates the components of the ink composition. It contains a non-white pigment dispersion that does not aggregate due to water, a resin dispersion that aggregates with a reaction liquid, and water. When the pigment is attached to the fabric, the fabric is printed and a printed product (printed product) is formed.

  Hereinafter, components contained in the non-white inkjet printing ink composition according to the present embodiment (hereinafter also simply referred to as “non-white printing ink composition” or “non-white ink”) will be described.

  In the present embodiment, the non-white pigment dispersion and the resin dispersion exemplified below are confirmed to be reactive with the reaction solution in the “reactivity confirmation test” and do not aggregate if the non-white pigment dispersion. What does not react (react) and what aggregates (reacts) should just be a resin dispersion. The non-white ink may be any non-white ink including non-white as a coloring material, and the non-white ink is not white, and examples thereof include cyan, magenta, yellow, black, green, red, orange, and blue. It is done.

  As a test for confirming the reactivity of the non-white pigment dispersion and the resin dispersion with the reaction liquid, for example, when dropping the pigment dispersion or the resin dispersion with a dropper from above the glass bottle containing the reaction liquid, In addition, the pigment dispersion or resin dispersion solidifies and separates from the reaction liquid, and agglomerates that float on the water surface or sink to the bottom of the bottle, and do not react even if the resin touches the reaction liquid. , Without clear separation, the whole dissolved or cloudy mixture will not aggregate. Here, the reaction liquid refers to the above-mentioned reaction liquid, and is used by being attached to a fabric together with the ink composition of the present embodiment.

1.3.1. Non-White Pigment Dispersion The non-white ink used in the ink jet textile printing method according to this embodiment includes a non-white pigment dispersion (hereinafter also simply referred to as “pigment”) that does not aggregate due to the reaction liquid as a coloring material.

  Here, the pigment dispersion refers to a color material in which pigment particles are dispersed in advance. When preparing the ink composition, a pigment dispersion in which a pigment is dispersed in advance is prepared, and the pigment dispersion is added to the ink composition, whereby the pigment can be uniformly dispersed. As a method of obtaining such a pigment dispersion, a method of dispersing a self-dispersed pigment in a dispersion medium without using a dispersant, a method of dispersing a pigment in a dispersion medium using a polymer dispersant, and a surface treatment are performed. There is a method of dispersing a pigment in a dispersion medium. Furthermore, you may disperse | distribute with a bead mill, a roll mill, etc. as needed. And in order to remove the particle | grains of the fixed size or more which may be contained in the pigment dispersion finally obtained, you may perform filter filtration or centrifugation. In addition, when performing filter filtration, the pore size (mesh size) of the filter is appropriately selected so that the particle size of the particles contained in the pigment dispersion is adjusted to a predetermined particle size as necessary. May be.

  The pigment contained in the pigment dispersion is not particularly limited as long as it is a non-white pigment dispersion that does not aggregate in the confirmation test with the above-described reaction liquid, and any of inorganic pigments and organic pigments can be used. Examples of the pigment include organic pigments such as azo, phthalocyanine, condensed polycyclic, nitro, nitroso, hollow resin particles, and polymer particles (brilliant carmine 6B, lake red C, watching red, disazo yellow, hansa). Yellow, phthalocyanine blue, phthalocyanine green, alkali blue, aniline black, etc.); metals such as cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese, nickel, titanium oxide, zinc oxide, antimony oxide, Metal oxides and sulfides such as zinc sulfide and zirconium oxide, and carbon blacks (CI pigment black 7) such as furnace carbon black, lamp black, acetylene black, and channel black, as well as loess, ultramarine blue, And bitumen etc. It can be used as the inorganic pigment.

Examples of carbon black used as a black pigment include No. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B etc. (above, manufactured by Mitsubishi Chemical Corporation), Raven
5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700 and the like (manufactured by Columbia Carbon Co., Ltd.), Rega1 400R, Rega1 330R, Rega1 660R, MoguL L, Monarch 800, Monarch 800, Monarch 800, 80 Monarch 1000, Monarch 1100, Monarch
1300, Monarch 1400, etc. (above, manufactured by Cabot Corporation), Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color
B1ack S150, Color Black S160, Color Black
S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 manufactured by Degussa, etc.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 167, 172, 180 and the like.

  Examples of magenta pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50 and the like.

  Examples of cyan pigments include C.I. I. Pigment blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, and the like.

  Examples of pigments other than black, white, yellow, magenta and cyan include C.I. I. Pigment green 7, 10, C.I. I. Pigment brown 3, 5, 25, 26, C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63 and the like.

  In the present embodiment, the non-white pigment dispersion that does not aggregate with the reaction liquid is a non-resin dispersant having a lower molecular weight than the resin contained in the resin dispersant or a pigment dispersed with a nonionic resin dispersant. It is preferable.

  As the non-resin dispersant, a non-resin surfactant or other low molecular weight dispersant can be used, and among these, nonionic non-resin dispersants are preferable. Non-resin dispersants can also be used. In this case, the resin dispersant has a molecular weight of 10,000 or more, and the non-resin dispersant has a molecular weight of less than 10,000, preferably 5000 or less, more preferably 3000 or less, still more preferably 1000 or less, particularly preferably. 500 or less, more preferably 300 or less.

As such a non-resin dispersant, for example, a non-resin surfactant can be used among the surfactants exemplified in the above reaction solution. Examples of such dispersants include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, and polyglycerin fatty acid. Ester, polyoxyethylene sorbite fatty acid ester, polyoxyethylene sterol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene fatty acid amide, polyoxyethylene polyoxypropylene block copolymer, tetramethyldecynediol, tetramethyldecynediol ethylene oxide addition Such as things.

  Moreover, a nonionic resin dispersant can be used. Such resin dispersants are composed of resins such as acrylic resins (including copolymers of acrylic and other monomers), urethane resins, polyether resins, polyester resins, polyamine resins, and the like. And those produced by controlling so as not to have an ionic group such as a group in the molecule. Moreover, resin which does not have an acid value is mentioned. These may be used alone or in combination.

  In addition, since the self-dispersing pigment generally tends to aggregate, it is difficult to use as a pigment of the textile printing ink composition according to the present embodiment. However, even if it is a self-dispersing pigment, it is possible to use a pigment that has been confirmed not to aggregate in the confirmation test of reactivity with the above-described reaction liquid. Examples of such a self-dispersing pigment include pigments that have been dispersed using the above-described dispersant and that have been confirmed not to agglomerate in the reactivity confirmation test with the aforementioned reaction liquid.

  These exemplified pigments may be used as a mixture of plural kinds. The content of the pigment dispersion in the textile printing ink composition varies depending on the pigment type, but from the viewpoint of obtaining good color developability, it is preferable when the total mass of the ink composition is 100% by mass as the pigment solid content. Is 1% by mass or more and 10% by mass or less, and the lower limit is more preferably 2% by mass or more, and further preferably 3% by mass or more. The upper limit value is more preferably 8% by mass or less, and more preferably 7% by mass or less.

1.3.2. Resin Dispersion The non-white printing ink composition according to this embodiment includes a resin dispersion that aggregates with a reaction liquid. The resin fine particles are resin contained in the resin dispersion. By forming a resin film, the resin fine particles have the function of improving the fixability of the image formed by the ink composition, and improve the wash fastness and friction fastness of the image. Can be made. As the resin dispersion, any of the emulsion state and the solution state can be used, but from the viewpoint of suppressing the increase in the viscosity of the ink, it is preferable to use the emulsion state.

  The resin contained in the resin dispersion is not particularly limited. For example, (meth) acrylic resin, styrene-acrylic resin, fluorene resin, urethane resin, olefin resin, rosin-modified resin, terpene resin, polyester resin, polyamide resin, epoxy Examples thereof include resins, vinyl chloride resins, and vinyl acetate resins. These resins may be used alone or in combination of two or more. Among these resins, a urethane resin is preferable from the viewpoint of excellent fixability of the pigment to the fabric.

  The urethane-based resin is not particularly limited as long as it has a urethane skeleton and has water dispersibility. For example, Superflex 460, 460s, 840 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Resamine D-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (trade name, manufactured by Dainichi Seika Kogyo Co., Ltd.), Takerak WS-5000, WS-6021, W-512-A Commercial products such as -6 (trade name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) and Suncure 2710 (trade name, manufactured by LUBRIZOL) may be used.

In addition, the urethane-based resin has a carboxy group, a sulfo group, a hydroxy group, etc. from the viewpoint of the storage stability of the ink, and from the viewpoint of improving the reactivity with the above-described reaction liquid when it contains a polyvalent metal compound. An anionic urethane-based resin having an anionic functional group of Among the above-mentioned commercially available products, examples of anionic urethane resins include Superflex 460, 460s, 840 manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; Takelac WS-5000, WS-6021 manufactured by Mitsui Chemicals Polyurethanes Co., Ltd. , W-512-A-6, and the like.

  In addition to the urethane bond, the urethane resin includes a polyether type urethane resin containing an ether bond in the main chain, a polyester type urethane resin containing an ester bond in the main chain, a polycarbonate type urethane resin containing a carbonate bond in the main chain, Etc. can be used. These urethane resins can be used in combination of multiple types.

  As the acrylic resin, polymers of acrylic monomers such as acrylic acid and acrylate esters, copolymers of acrylic monomers with other monomers, and the like can be used. Examples of the monomer include vinyl monomers such as styrene. Commercially available products may be used as the acrylic resin, and examples thereof include mobile 702, 7502, 7525, 7320 (manufactured by Nippon Synthetic Chemical Co., Ltd.).

  Further, the resin contained in the non-white textile printing ink composition according to the present embodiment may be a self-dispersion type (self-emulsification type) into which a hydrophilic component necessary for stable dispersion in water is introduced, or external It may be water-dispersible by the use of an emulsifier, but when it includes a step of attaching a reaction liquid containing an aggregating agent that aggregates the components of the ink composition to the fabric, a polyvalent metal salt contained in the reaction liquid and From the viewpoint that it is difficult to inhibit this reaction, a self-dispersing dispersion containing no dispersant (self-dispersing emulsion) is preferable. In addition, the above-mentioned confirmation test shows how much the functional group that the resin aggregates in the reaction solution has in the molecule and how much the acid value of the resin is related to the aggregation property. You can confirm by the method.

  The resin content is preferably 1% by mass or more and 15% by mass or less in terms of solid content with respect to the total mass (100% by mass) of the non-white ink composition, and the lower limit is 2.0% by mass. More preferably, it is more preferably 3% by mass or more. Further, the upper limit value of the content of the resin fine particles is more preferably 12% by mass or less, and further preferably 10% by mass or less. By setting the content of the resin fine particles in the above range, it is possible to achieve both the color developability and the washing fastness of the obtained recorded matter.

1.3.3. Water The non-white printing ink composition used in this embodiment contains water as a solvent. Water is a main medium of ink and is a component that evaporates and scatters when dried. Examples of water include water from which ionic impurities have been removed as much as possible, such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and ultrapure water. Further, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of mold and bacteria can be prevented when the ink is stored for a long time.

  The content of water contained in the non-white textile printing ink composition is not particularly limited, but may be, for example, 50% by mass or more, further 60% by mass with respect to the total mass of the ink. It can be above, and it can be 70 mass% or more. Further, the upper limit of the content of water contained in the ink can be 95% by mass or less, 90% by mass or less, and 80% by mass or less.

1.3.4. Water-soluble organic solvent In the present embodiment, the non-white printing ink composition may contain a water-soluble organic solvent. By including the water-soluble organic solvent, it is possible to effectively suppress the evaporation of moisture from the ink-jet head when the ink composition is left standing for a long time while improving the ejection stability of the ink composition by the ink-jet method.

  Examples of the water-soluble organic solvent include polyol compounds, glycol ethers, betaine compounds, and the like.

  Examples of the polyol compound include a polyol compound (preferably a diol compound) having 2 to 6 carbon atoms in the molecule and having one ether bond in the molecule. Specific examples include 1,2-pentanediol, methyl triglycol (triethylene glycol monomethyl ether), butyl triglycol (triethylene glycol monobutyl ether), butyl diglycol (diethylene glycol monobutyl ether), dipropylene glycol monopropyl ether Glycerin, 1,2-hexanediol, 1,2-heptanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butane Diol, 2-methyl-3-phenoxy-1,2-propanediol, 3- (3-methylphenoxy) -1,2-propanediol, 3-hexyloxy-1,2-propanediol, 2-hydroxymethyl- 2-phenoxymethyl- , 3-propanediol, 3-methyl-1,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,4-butanediol, 1,5-pentane Examples include glycols such as diol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, and 3-methyl-1,5-pentanediol.

  Examples of glycol ethers include monoalkyl ethers of glycols selected from ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol. preferable. More preferably, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monopropyl ether and the like can be mentioned.

  A betaine compound is a compound that has a positive charge and a negative charge at non-adjacent positions in the same molecule, and has no positively charged hydrogen atoms bonded to dissociable hydrogen atoms, so that the molecule as a whole has no charge. (Inner salt). Preferred betaine compounds are N-alkyl substituted amino acids, more preferably N-trialkyl substituted amino acids. Examples of the betaine compound include trimethylglycine (also referred to as “glycine betaine”), γ-butyrobetaine, homarine, trigonelline, carnitine, homoserine betaine, valine betaine, lysine betaine, ornithine betaine, alanine betaine, stachydrine, and glutamic acid betaine. Preferably, a trimethylglycine etc. can be illustrated.

  A pyrrolidone derivative may be used as the water-soluble organic solvent. Examples of pyrrolidone derivatives include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-butyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone. Etc.

  A plurality of water-soluble organic solvents may be used in combination. The total amount of the water-soluble organic solvent is preferably added so as to have the desired viscosity and surface tension of the ink described later, and is 0.2% by mass or more and 30% by mass with respect to the total amount of the ink composition. % Or less, preferably 0.4% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, and further preferably 0.7% by mass or more and 10% by mass or less.

1.3.5. Surfactant The non-white printing ink composition according to this embodiment may contain a surfactant. As the surfactant, any of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used, and these may be used in combination. The surfactant can reduce the interfacial tension of the ink composition and increase the permeability to the fabric. Specific examples of the surfactant are the same as those described in the section of the reaction solution. However, since the cationic surfactant may aggregate the components of the textile printing ink composition, it is more preferable to use a small amount of surfactant or another type of surfactant.

  When a surfactant is added to the non-white printing ink composition, the total amount of the surfactant is 0.01% by mass or more and 3% by mass or less, preferably 0.05% with respect to the entire non-white printing ink composition. It is preferably blended in an amount of not less than 2% by mass and not more than 2% by mass, more preferably not less than 0.1% by mass and not more than 1% by mass, particularly preferably not less than 0.2% by mass and not more than 0.5% by mass.

  When the non-white textile printing ink composition contains a surfactant, the stability when ejecting ink from the head is increased. Moreover, the use of an appropriate amount of the surfactant improves the permeability to the fabric and can increase the contact with the reaction solution. Thereby, aggregation of the resin dispersion and thickening of the printing ink composition are likely to occur, and the color development of the printed product can be further improved. When a surfactant is added to the ink in excess of an appropriate amount, the excess surfactant may bleed out after printing, and the fastness of the printed image may be insufficient.

1.3.6. Other Components The non-white textile printing ink composition according to the present embodiment may contain a pH adjuster, an antiseptic / fungicide, a rust inhibitor, a chelating agent, and the like as necessary.

<PH adjuster>
Examples of the pH adjuster include potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia, diethanolamine, triethanolamine, triisopropanolamine, potassium carbonate, sodium carbonate, Examples thereof include sodium hydrogen carbonate.

<Preservatives and fungicides>
Examples of preservatives and fungicides include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzthiazoline-3-one (ICI) Proxel CRL, Proxel BND, Proxel GXL, Proxel XL-2, Proxel TN) and the like.

<Chelating agent>
Chelating agents have the property of trapping ions. Examples of such a chelating agent include ethylenediaminetetraacetate (EDTA), ethylenediamine nitrilotriacetate, hexametaphosphate, pyrophosphate, and metaphosphate.

1.3.7. Preparation method of non-white ink composition The non-white printing ink composition used in the present embodiment is obtained by mixing the components described above in an arbitrary order, and removing impurities by filtering or the like as necessary. . As a method for mixing the components, a method in which materials are sequentially added to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed is suitably used. As a filtration method, centrifugal filtration, filter filtration, or the like can be performed as necessary.

1.3.8. Physical Properties of Non-White Ink Composition The non-white printing ink composition according to this embodiment is applied to a fabric by an ink jet method. For this reason, the textile printing ink composition preferably has a surface tension at 25 ° C. of 10 mN / m or more and 40 mN / m or less from the viewpoint of the balance between the recording quality and the reliability as an ink for ink jet recording. More preferably, it is 40 mN / m or less.

  From the same viewpoint, the viscosity at 20 ° C. of the non-white printing ink composition is preferably 2 mPa · s to 15 mPa · s, more preferably 2 mPa · s to 5 mPa · s, and more preferably 2 mPa · s. -More preferably, it is s or more and 3.6 mPa * s or less.

  In addition, the non-white printing ink composition according to the present embodiment can be used as an ink set containing the reaction liquid and the printing ink composition, and in addition to the non-white printing ink composition, A white textile printing ink composition may be included. In this case, white pigments contained in the white textile printing ink composition include C.I. I. Pigment White 1 (basic lead carbonate), 4 (zinc oxide), 5 (mixture of zinc sulfide and barium sulfate), 6 (titanium oxide), 6: 1 (titanium oxide containing other metal oxides), 7 (Zinc sulfide), 18 (calcium carbonate), 19 (clay), 20 (titanium mica), 21 (barium sulfate), 22 (natural barium sulfate), 23 (gloss white), 24 (alumina white), 25 (gypsum) ), 26 (magnesium oxide / silicon oxide), 27 (silica), 28 (anhydrous calcium silicate), and the like.

1.4. White Inkjet Textile Ink Composition In the inkjet textile printing method according to the present embodiment, in addition to the above-described non-white inkjet textile ink composition, a white inkjet textile ink composition (hereinafter also simply referred to as “white ink”) is provided. An ink set may be used.

  The white ink composition only needs to include a white pigment instead of the non-white pigment contained in the above-described non-white ink composition. Examples of the white pigment include titanium oxide, alumina oxide, and silica. Examples thereof include inorganic metal compounds and white pigments such as hollow resin fine particles.

  The content of the white pigment contained in the white ink composition is preferably 5% by mass or more and 25% by mass or less, and more preferably 7% by mass or more and 20% by mass with respect to the white ink composition in terms of excellent color developability. % Or less, more preferably 8% by mass or more and 15% by mass or less.

  Examples of components other than the white pigment contained in the white ink composition include those that may be contained in the above-described non-white ink composition. However, when resin fine particles (resin dispersion) are included, the resin fine particles are not limited to agglomeration. The white ink composition preferably contains a white pigment and resin fine particles, and the cohesiveness of the white pigment and resin fine particles contained in the reaction liquid is not limited, but in terms of excellent color developability, Aggregation of at least one of the resin fine particles is preferable in terms of excellent color developability and a high degree of freedom in designing a white ink composition. The preparation method and physical properties of the white ink composition are also the same as those of the above-described non-white ink composition.

1.5. Inkjet Textile Printing Method Next, the inkjet textile printing method according to this embodiment will be described for each process. The ink jet textile printing method according to this embodiment includes a step of attaching a reaction liquid to a fabric and a step of attaching a non-white ink jet textile ink composition to the fabric by an ink jet method.

1.5.1. Reaction liquid adhesion process The reaction liquid adhesion process is a process in which a reaction liquid for aggregating the components of the ink composition is adhered to the cloth before the ink adhesion process in which the ink composition is discharged and adhered to the cloth.

As the reaction solution, the above-described reaction solution can be used. Adhesion amount of the reaction liquid is preferably, for example, it is attached such that the 0.02 g / cm ² or more 0.5 g / cm ² or less, 0.02 g / cm ² or more 0.24 g / cm ² or less and so as It is more preferable to adhere to. By setting the amount of the reaction solution to be within the above range, it becomes easy to uniformly apply the reaction solution to the fabric, and it is possible to suppress the uneven aggregation of the image and enhance the color development.

Further, in the reaction solution attaching step, the amount of the polyvalent metal salt contained in the reaction solution attached to the fabric is preferably attached so as to be 1.6 μmol / cm ² or more and 6 μmol / cm ² or less. it is more preferable to adhere to the cm ² or more 5 [mu] mol / cm ² or less. By attaching the polyvalent metal salt so that the amount of the polyvalent metal salt is 1.6 μmol / cm ² or more, the color developability of the recorded image is improved. In addition, by attaching the polyvalent metal salt so that the adhesion amount is 6 μmol / cm ² or less, the fastness to washing of the recorded image is improved.

  Examples of the method of attaching the reaction liquid to the cloth include a method of immersing the cloth in the reaction liquid (dip coating), a method of applying the reaction liquid with a roll coater (roller coating), and spraying the reaction liquid with a spray device or the like. A method of spraying (spray coating), a method of spraying the reaction liquid by an ink jet method (ink jet coating), and the like, and any method may be used.

  The inkjet printing method according to the present embodiment may include a reaction liquid drying step of drying the reaction liquid attached to the fabric after the reaction liquid attachment step. The reaction solution may be dried by natural drying, but drying with heating is preferable from the viewpoint of improving the drying speed. When heating is performed in the drying step of the reaction solution, the heating method is not particularly limited, and examples thereof include a heat press method, a normal pressure steam method, a high pressure steam method, and a thermofix method. Moreover, as a heat source of heating, although not limited to the following, infrared (lamp) is mentioned, for example.

1.5.2. Ink attachment step The ink attachment step is a step in which the non-white printing ink composition is attached to the fabric by the ink jet method in at least a part of the region where the reaction solution is attached in the reaction solution attachment step. An image is recorded on the cloth by adhering droplets to the cloth. As a result, the resin dispersion contained in the textile printing ink composition reacts with or interacts with the components of the reaction solution, thereby aggregating the resin dispersion, thereby suppressing aggregation unevenness, excellent color development, and fastness to washing. An image with excellent properties can be obtained.

  As the ink jet recording method for discharging the non-white textile printing ink composition, any method may be used, and examples thereof include a charge deflection method, a continuous method, an ondenmand method (piezo method, bubble jet (registered trademark) method), and the like. Among these ink jet recording systems, a system using a piezo type ink jet recording apparatus is more preferable from the viewpoints of high definition and downsizing of the apparatus.

In the inking process, the maximum deposition amount of the non-white ink composition is preferably be attached to the fabric so that 30 mg / cm ² or less, more preferably 20 mg / cm ² or less, 15 mg / cm ² or less Is more preferable, and it is more preferable to make it adhere so that it may become 10 mg / cm < ² > or less. When the adhesion amount of the non-white ink composition is as described above, the aggregation unevenness is suppressed while improving the color development of the image, and the image quality is improved. The lower limit of the maximum adhesion amount of the ink composition is preferably 1.5 mg / cm ² or more, more preferably 2 mg / cm ² or more, more preferably 3 mg / cm ² or more It is particularly preferably 5 mg / cm ² or more. In this case, the color developability of the recorded image is good, and it is possible to record images such as pictures and characters on the fabric with good reproducibility.

  In this embodiment, in addition to the non-white ink composition described above, it may be used as an ink set further comprising a white ink composition. In this ink attaching step, the step of attaching the white ink composition to the fabric by an inkjet method You may prepare further

The maximum amount of the white ink composition attached to the fabric is preferably 50 mg / cm ² or more and 200 mg / cm ² or less, and preferably 80 mg / cm ² or more and 150 mg / cm ² or less. more preferably be deposited, it is attached such that the 90 mg / cm ² or more 130 mg / cm ² or less still more preferred to. When the maximum adhesion amount of the white ink composition is as described above, the white color developability is good, and the color development particularly when adhering to a dark fabric is excellent, which is preferable as a background image. Moreover, it is preferable that the adhesion amount is in the above range because the fastness of the image is excellent and the aggregation unevenness tends to be inconspicuous. Further, not only the maximum adhesion amount of the white ink composition, but also the adhesion amount in the adhesion step is preferably in the above range.

1.5.3. Step of Heating Fabric The ink-jet printing method according to the present embodiment preferably includes a heating step of heating the ink composition (image) attached to the fabric.

  The heating method for heating the ink composition applied to the fabric is not particularly limited, and examples thereof include a heat press method, a normal pressure steam method, a high pressure steam method, a hot air drying method, and a thermofix method. . Moreover, as a heat source of heating, although not limited to the following, infrared (lamp) is mentioned, for example.

  The heating temperature for heating the ink composition adhered to the fabric is not limited to this, but is preferably 80 ° C. or higher and 200 ° C. or lower, and preferably 100 ° C. or higher and 180 ° C. or lower. More preferred. When the heating temperature is within the above range, damage to the fabric can be reduced, and film formation of the resin contained in the ink composition can be promoted. The heating time is not limited to this, but it can be, for example, 30 seconds or more and 20 minutes or less, preferably 2 minutes or more and 7 minutes or less, more preferably 3 minutes or more and 5 minutes or less. It is. When the heating time is within the above range, it is possible to sufficiently dry the ink while reducing the damage to the fabric. In addition, in this process, heating temperature means the temperature of the image surface formed in the fabric, for example, is measured using a non-contact thermometer (trade name “IT2-80”, manufactured by Keyence Corporation). be able to.

  In addition to the main heating step, a step of heating the fabric may be provided before the ink attaching step or at the time of the ink attaching step. If the fabric is heated during the ink adhering step, the viscosity and the surface tension are lowered due to the high temperature of the ink, and the ink tends to spread evenly and penetrate into the fabric. As a result, the ink is easily fixed on the fabric, the leveling property of the obtained recorded matter is improved, the aggregation unevenness is suppressed, the coloring property is high, and an image excellent in washing fastness can be obtained. Moreover, by allowing the ink composition to adhere to the heated fabric, the drying property of the ink can be improved, the drying time after the ink is adhered can be shortened, and the damage to the fabric can be reduced. it can.

  As described above, according to the inkjet printing method according to the present embodiment, the non-white printing ink composition includes the non-white pigment dispersion that does not aggregate with the reaction liquid and the resin dispersion that aggregates with the reaction liquid. Thus, the reaction liquid adhering to the fabric reacts with the resin dispersion instead of the non-white pigment dispersion in the ink, and thus improves the image quality by suppressing aggregation unevenness while improving the color of the obtained image, An image excellent in washing fastness can be obtained.

2. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited only to these examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.

2.1. Preparation of reaction liquid Each component was mixed and stirred so that the mixture ratio of Table 1 might be obtained, and reaction liquid AC was obtained. In Table 1 below, the unit of numerical values is mass%, and ion-exchanged water was added so that the total mass of the reaction solution was 100 mass%.

Details of the components shown in Table 1 are as follows.
PAA-SA (trade name, manufactured by Nitto Bo Medical Co., Ltd., cationic polyallylamine amide sulfate polymer)

2.2. Preparation of ink composition First, pigment dispersions 1 to 4 were prepared.

<Pigment dispersion 1>
Pigment dispersion 1: P.R.122 was used as a pigment, and nonionic styrene-acrylic resin was used as a pigment dispersant. Specifically, a resin obtained by polymerization using 55% by mass of styrene as a nonionic styrene-acrylic resin and 45% by mass of acrylic acid ester (butyl acrylate) as an acrylic monomer having no carboxyl group was used. After mixing with 3 parts by mass of pigment using 1 part by mass of dispersant and 10 parts by mass of ion-exchanged water and premixing the resulting mixture, a bead mill disperser (UAM-015, manufactured by Kotobuki Industries Co., Ltd.) is used. Used, dispersed with zirconia beads having a diameter of 0.03 mm at a peripheral speed of 10 m / s and a liquid temperature of 30 ° C. for 15 minutes, and then the coarse particles are centrifuged with a centrifuge (Model 3600, manufactured by Kuboyama Corporation) to disperse the pigment. Body 1 was obtained.

<Pigment dispersion 2>
As the pigment, PR 122 was used in the same manner as the pigment dispersion 1. Using a polyoxyethylene (n = 40) β naphthyl ether as a pigment dispersant, a pigment dispersion 2 was obtained in the same manner as the pigment dispersion 1.

<Pigment dispersion 3>
As the pigment, PR 122 was used in the same manner as the pigment dispersion 1. An anionic resin dispersant was used as the pigment dispersion. Specifically, a resin obtained by synthesizing a styacrylic resin using 55% by mass of styrene, 20% by mass of acrylic acid, and 30% by mass of methyl methacrylate was used. Using the obtained resin, Pigment Dispersion 3 was obtained in the same manner as Pigment Dispersion 1.

<Pigment dispersion 4>
Using titanium oxide as the pigment and using a nonionic urethane resin as the dispersant, Pigment Dispersion 4 was obtained in the same manner as Pigment Dispersion 1.

  Next, using the obtained pigment dispersion, the components shown in Table 2 were mixed, mixed and stirred with a magnetic stirrer for 2 hours, and then filtered using a membrane filter having a pore size of 5 μm to obtain inks 1 to 9 Got. In Table 2 below, the unit of numerical values is mass%, and the ion exchange water was added so that the total mass of the ink was 100 mass%.

Details of components other than the pigment dispersion shown in Table 2 are as follows.
-Takelac WS-6061 (trade name, manufactured by Mitsui Chemicals Polyurethanes, anionic urethane resin emulsion, self-emulsifying type, solid content 30%)
-Takelac WS-6021 (trade name, manufactured by Mitsui Chemicals Polyurethanes, anionic self-dispersing urethane resin emulsion, self-emulsifying type, solid content 30%)
-Takelac WS-5000 (trade name, manufactured by Mitsui Chemicals Polyurethanes, anionic self-dispersing urethane resin emulsion, self-emulsifying type, solid content 30%)
・ BYK-348 (trade name, manufactured by BYK Japan Japan, polysiloxane surfactant)

  Here, the confirmation of the reactivity (cohesiveness) of the pigment and the resin and the storage stability test of the ink were performed as follows.

<Reactivity confirmation test>
15 cc of the reaction solution was placed in a 30 cc glass bottle. Each pigment dispersion or resin dispersion is dropped with a dropper from above, and when dropped, the pigment dispersion or resin dispersion solidifies and separates from the reaction liquid and floats on the water surface or sinks to the bottom of the bottle Those that become were considered reactive. On the other hand, when a pigment dispersion or resin dispersion is dropped with a dropper, it does not react even if the pigment dispersion or resin dispersion touches the reaction solution, and it does not separate clearly and dissolves or becomes cloudy throughout. Those that did not were reactive.

<Ink storage stability test>
The ink was stored at 60 ° C. for 7 days, and the rate of increase in viscosity with respect to the initial value was measured at a viscosity of 25 ° C. The viscosity was measured using a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica) and evaluated according to the following criteria.
○: Increase in viscosity is 2% or less △: Increase in viscosity exceeds 2%

2.3. Evaluation Test Next, evaluation samples shown in Table 3 according to Examples and Comparative Examples used in the following evaluation tests were prepared as follows.

<Recording test>
A modified machine of SC-F2000 (manufactured by Seiko Epson Corporation) was prepared as an ink jet textile printing apparatus, and ink was filled in one nozzle row. First, the reaction solution was uniformly spray-coated on the fabric at a coating amount of 3 g per A4 size. After spray application, the fabric was sufficiently dried by heating at 60 ° C. for 5 minutes. Next, a fabric was set on the printer, and ink was ejected from the head to adhere to the test pattern. The recording resolution of the ink was 1440 × 1440 dpi, and the ink adhesion amount was the value shown in Table 3. After adhesion, the fabric discharged from the printer was post-heated at 120 ° C. for 1 minute. In addition, 100% cotton white fabric (heavy weight manufactured by Hanes) was used as the fabric.

<Evaluation of color development (density)>
The pattern portion of the recorded matter obtained in the recording test was visually evaluated.
○: The color of the comparative fabric is not visible and is colored with the ink color.
Δ: The color of the fabric looks slightly blurred
X: The color of the fabric is quite visible.

<Evaluation of fastness to washing>
The recorded matter was evaluated by a wash fastness test. The washing fastness test was performed according to “AATCC 61 2A, 3A” and visually evaluated according to the following evaluation criteria. The following “2A” indicates that washing was performed at 25 ° C., and “3A” indicates that washing was performed at 60 ° C.
◯: There was no dropout of the coating film in the pattern portion under both 2A and 3A conditions.
(Triangle | delta): There is no omission of a coating film in 2A. In 3A, there was a slight dropout.
X: The coating film dropped off at 2A.

<Coagulation unevenness>
The pattern portion of the recorded matter obtained in the recording test was visually evaluated.
○: The pattern is not rough.
X: Unevenness with a rough color appears in the pattern.

2.4. Evaluation results Table 3 shows the results of the above evaluation tests.

  As shown in Table 3, in Examples 1 to 9, all were excellent in coloring property, fastness to washing, and reduction in aggregation unevenness. On the other hand, Comparative Example 1 does not include a resin dispersion that aggregates with the reaction liquid, resulting in poor color development. In Comparative Examples 2 and 3, the ink includes a pigment dispersion that aggregates with the reaction liquid. The result was inferior in fastness and reduction in aggregation unevenness. Further, in Comparative Example 4, since no reaction solution was used, the color development was inferior. From Examples 1, 2, and 3, the coagulant contained in the reaction solution was preferably a polyvalent metal salt. From Examples 1 and 4, as for the pigment dispersant, the nonionic styrene-acrylic resin has higher storage stability and higher color developability. From Examples 1 and 5, as the resin dispersion contained in the ink, the resin 2 was higher in washing fastness. From Examples 1 and 6, when the amount of the pigment dispersion contained in the ink was small, the color development was reduced. From Examples 1 and 7, when the amount of the resin dispersion contained in the ink is small, the wash fastness is lowered.

In Reference Example 1 using a white pigment as the pigment, the white pigment adheres to the dark fabric as a base image with a high adhesion amount, indicating that color development, fastness to washing, and reduction in aggregation unevenness tend to be good. However, in Reference Example 2, since the reaction solution was not used, the color development was inferior. Further, from comparison between Example 8 and Example 1, it was found that when the ink composition adhesion amount is relatively small, washing fastness and color development tend to be lowered. Further, from comparison between Example 9 and Example 5, it was found that even when the ink composition adhesion amount was increased to 30 mg / inch ² , the wash fastness was Δ and the results were the same.

Although not shown in the table, a test was conducted in the same manner as in Comparative Example 2 except that the ink composition adhesion amount was set to 100 mg / inch ² in Comparative Example 2. The unevenness was both good (◯), but the amount of the non-white ink composition attached to the fabric was large, and it was not suitable for recording delicate images such as pictures and characters.

  In addition, by performing the recording test of Example 1 and the recording test of Reference Example 1 on one fabric, the non-white ink composition and the white ink composition are excellent in coloring property, washing fastness, and reduction in aggregation unevenness, respectively. I was able to record.

  As described above, an ink-jet printing ink composition used by adhering to a fabric together with a reaction liquid for aggregating the components of the ink composition, a non-white pigment dispersion that does not aggregate with the reaction liquid, and a resin dispersion that aggregates with the reaction liquid And non-white ink-jet printing ink composition containing water, improving the image quality by suppressing aggregation unevenness while improving the color of the obtained image, and improving the fastness to washing It was found that an excellent image can be obtained.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (10)

An ink-jet printing ink composition used by adhering to a fabric together with a reaction liquid for aggregating the components of the ink composition,
A non-white inkjet printing ink composition comprising: a non-white pigment dispersion that does not aggregate with the reaction liquid; a resin dispersion that aggregates with the reaction liquid; and water. 2. The non-white inkjet printing ink composition according to claim 1, wherein the non-white inkjet printing ink composition is used by being attached to the fabric with a maximum adhesion amount of 30 mg / inch ² or less.   The non-white inkjet printing ink composition according to claim 1 or 2, wherein the non-white pigment dispersion is obtained by dispersing a pigment with at least one of a non-resin dispersant and a nonionic resin dispersant.   The non-white inkjet printing ink composition according to claim 3, wherein the nonionic resin dispersant is used.   The non-white inkjet printing ink composition according to claim 1 or 2, wherein the resin dispersion is a self-dispersing resin dispersion.   The content of the non-white pigment dispersion is 1% by mass or more and 7% by mass or less, and the content of the resin dispersion is 1% by mass or more and 15% by mass or less. 2. The non-white inkjet printing ink composition according to item 1.   The non-white inkjet printing ink composition according to any one of claims 1 to 6, wherein the reaction liquid contains at least one of a polyvalent metal salt, an organic acid, and a cationic resin as an aggregating agent.   A non-white inkjet printing ink composition comprising a step of attaching a reaction liquid to a fabric, a non-white pigment dispersion that does not aggregate with the reaction liquid, a resin dispersion that aggregates with the reaction liquid, and water. An ink-jet printing method comprising: adhering to a fabric by the method.   Furthermore, the inkjet textile printing method of Claim 8 provided with the process of making the white inkjet textile printing ink composition containing a white pigment adhere to a fabric by the inkjet method. The inkjet according to claim 9, wherein the maximum adhesion amount of the non-white inkjet printing ink composition is 30 mg / inch ² or less, and the maximum adhesion amount of the white inkjet printing ink composition is 50 mg / inch ² or more. Printing method.