阅读说明：本技术 处理液组合物、喷墨印染方法以及布帛 (Treatment liquid composition, inkjet printing method, and fabric ) 是由 冈田英树 藤江俊浩 大桥正和 于 2018-06-11 设计创作，主要内容包括：提供一种抑制了预处理痕迹的产生的处理液组合物、喷墨印染方法以及布帛。本发明的处理液组成物为在印染中附着于布帛(2)来使用的处理液组成物,并含有阳离子性化合物、甜菜碱和水。(Provided are a treatment liquid composition, an ink jet printing method, and a fabric, wherein the occurrence of a pretreatment mark is suppressed. The treatment liquid composition of the present invention is used by adhering to a fabric (2) in printing, and contains a cationic compound, betaine, and water.)

1. A treatment liquid composition for use in adhering to a fabric in printing, the treatment liquid composition comprising:

a cationic compound;

betaine; and

and (3) water.

2. The treatment liquid composition according to claim 1,

the treating fluid composition is used for ink jet pigment printing and dyeing.

3. The treatment liquid composition according to claim 1 or 2,

the content of betaine is 0.2 or more in mass ratio to the content of the cationic compound.

4. The treatment liquid composition according to any one of claims 1 to 3,

the fabric is a cotton fabric colored with a dye.

5. The treatment liquid composition according to any one of claims 1 to 4,

the betaine is selected from more than one of L-carnitine, trimethylglycine and gamma-butyl betaine.

6. The treatment liquid composition according to any one of claims 1 to 5,

the content of betaine is 0.6 or more in mass ratio to the content of the cationic compound.

7. The treatment liquid composition according to any one of claims 1 to 6,

the content of betaine is 2.0 or less in mass ratio to the content of the cationic compound.

8. The treatment liquid composition according to any one of claims 1 to 7,

the cationic compound is a polyvalent metal salt.

9. The treatment fluid composition according to claim 8,

the cationic compound is a calcium salt.

10. The treatment liquid composition according to any one of claims 1 to 9,

the fabric contains a triazine compound.

11. The treatment liquid composition according to any one of claims 1 to 10,

further contains a surfactant, and the surfactant has an HLB value of 13 or more.

12. The treatment liquid composition according to claim 11,

the content of the surfactant is 0.3% by mass or less based on the total mass of the treatment liquid composition.

13. An ink-jet textile printing method characterized in that,

a process comprising attaching the treatment liquid composition according to any one of claims 1 to 12 to a fabric.

14. The ink jet printing method according to claim 13, wherein,

the method comprises a step of applying a pigment printing ink to a region of the fabric to which the treatment liquid composition is applied by an ink jet method.

15. A fabric characterized in that,

the fabric can be obtained by attaching the treatment liquid composition according to any one of claims 1 to 12.

Technical Field

The present invention relates to a treatment liquid composition, an inkjet printing method, and a fabric.

Background

Conventionally, in the dyeing of a base material such as a fabric with a coloring material, a technique of pretreating the base material with a treatment liquid containing a cationic compound or the like has been known in order to improve the color developability or the bleeding of the coloring material. For example, patent document 1 proposes a pretreatment agent for ink jet textile printing containing a polyvalent metal ion and specific polymer microparticles as such a treatment liquid.

Disclosure of Invention

Problems to be solved by the invention

However, it is also found that the use of the pretreatment agent for ink jet textile printing described in patent document 1 can improve color developability, but there is a problem that it is difficult to suppress the occurrence of a pretreatment mark. Specifically, when the fabric is pretreated with the pretreatment agent containing the polyvalent metal ion, a change in appearance, i.e., a pretreatment mark, which is visually recognized occurs in the area where the pretreatment agent is attached. It is understood that such a trace of pretreatment tends to be conspicuous on a fabric (cloth) colored in a deep color in advance with a dye or the like, and is easily expressed as a change in hue of the cloth color. When a fabric is pretreated, a pretreatment agent is often attached to the fabric outside the area where dyeing (printing) is performed using a color material. Thus, when a pretreatment mark is generated in an area where printing is not performed, a change in color or the like becomes more noticeable than in an area where pretreatment is not performed (an area where a pretreatment mark is not generated). Thus, the appearance quality of the product subjected to printing and dyeing manufacturing may be deteriorated due to the generation of the pretreatment mark.

Means for solving the problems

The present invention has been made to solve at least part of the above problems and is also proposed to improve color developability and suppress the occurrence of processing traces, and can be realized as the following embodiments or application examples.

[ application example ] the treatment liquid composition according to the present application example is a treatment liquid composition used for adhering to a fabric in printing and dyeing, and the treatment liquid composition contains a cationic compound, betaine, and water.

According to the present application example, the generation of the trace of the pretreatment can be suppressed in the fabric to which the treatment liquid composition is adhered by the pretreatment.

The treatment liquid composition described in the above application example is preferably used for ink jet pigment printing.

In this way, by performing ink jet pigment printing using a pigment as a color material, the color developability of the color material can be further improved. In addition, the process such as the dip dyeing process or the cleaning process can be simplified as compared with the dye. Further, it is possible to print and dye a wide variety of fibers compared to dyes in which the types of fibers (fabrics) that can be used are limited.

In the treatment liquid composition described in the above application example, the content of betaine to the content of the cationic compound is preferably 0.2 or more in mass ratio.

This can further suppress the generation of a trace of pretreatment.

In the treatment liquid composition described in the above application example, a cotton fabric colored with a dye is preferable.

Thus, the cotton fabric colored in advance with a dye, such as clothing or other accessories, can be prevented from generating a trace of pretreatment while ensuring color developability.

In the treatment liquid composition according to the application example, the betaine is preferably at least one selected from the group consisting of l-carnitine, trimethylglycine and γ -butylbetaine.

This can further suppress the generation of a trace of pretreatment.

In the treatment liquid composition described in the above application example, the content of betaine is preferably 0.6 or more in terms of a mass ratio to the content of the cationic compound.

This can further suppress the occurrence of pretreatment marks, and is particularly suitable for a red-colored fabric.

In the treatment liquid composition described in the above application example, the content of betaine to the content of the cationic compound is preferably 2.0 or less in terms of a mass ratio.

This suppresses an increase in wettability of the fabric. Therefore, when the fabric is printed with a color material, occurrence of strike-through of the color material is suppressed, and the color developability of the color material can be further improved.

In the treatment liquid composition according to the above application example, the cationic compound is preferably a polyvalent metal salt.

This promotes aggregation of the color material and the like, and can further improve the color developability of the color material. In addition, the fabric can be suitably used for cotton fabrics.

In the treatment liquid composition according to the above application example, the cationic compound is preferably a calcium salt.

This can further suppress the occurrence of a trace of pretreatment. In addition, the color developing property of the color material can be improved, and the color material can be more suitably used for cotton cloth.

In the treatment liquid composition described in the above application example, the fabric preferably contains a triazine compound.

The generation of a trace of pretreatment can be suppressed for a fabric (cloth) dyed with a triazine compound.

The treatment liquid composition described in the above application example preferably further contains a surfactant, and the surfactant has an HLB value of 13 or more.

Thus, when the treatment liquid composition is attached to a fabric, the penetration into the fabric and wet spreading can be controlled.

In the treatment liquid composition described in the above application example, the content of the surfactant is preferably 0.3% by mass or less with respect to the total mass of the treatment liquid composition.

This suppresses excessive reduction in the surface tension of the treatment liquid composition, and the treatment liquid composition is easily held in the vicinity of the surface of the fabric when adhering to the fabric. This makes it possible to easily express the function of the treatment liquid composition.

Application example the inkjet textile printing method according to the application example includes a process of attaching the treatment liquid composition described in the application example to a fabric.

According to the present application example, it is possible to provide an ink jet textile printing method in which the occurrence of a pretreatment mark is suppressed compared to the conventional method while ensuring color developability.

The ink jet textile printing method described in the above application example preferably includes a step of applying a pigment textile printing ink to a region of the fabric to which the treatment liquid composition is applied by an ink jet method.

This makes it easy to produce a large number of products in a small amount without using a plate or the like required for, for example, a dummy printing, and also makes it possible to form a highly fine image or the like. Further, by using the pigment printing ink, the color developability of the color material can be further improved, and the processes such as the padding process and the cleaning process can be simplified as compared with the dye ink. In addition, a wide variety of fibers can be printed with dyes that are limited in the types of fibers (fabrics) that can be used.

Application example the fabric according to the present application example can be obtained by attaching the treatment liquid composition described in the above application example.

According to the present application example, when used for printing, it is possible to provide a fabric in which occurrence of a pretreatment mark is suppressed more than in the prior art while color developability is ensured. That is, the appearance quality of the product subjected to printing and dyeing can be improved.

Drawings

FIG. 1 is a schematic perspective view showing an ink jet textile printing apparatus according to an embodiment.

Detailed Description

Hereinafter, embodiments of the present invention will be described. The embodiment described below is an embodiment illustrating an example of the present invention. The present invention is not limited to the following embodiments, and can be modified as appropriate within the scope not departing from the spirit or scope of the invention as can be understood from the scope of the claims and the entire specification, and the present invention is a treatment liquid composition, an inkjet printing method, and a fabric accompanied by such modification, or an invention included in the technical scope of the present invention.

< treatment liquid composition >

The treatment liquid composition of the present embodiment (hereinafter simply referred to as "treatment liquid") is used by adhering to a fabric serving as a base material of a printed matter in advance when the ink composition is applied (printed) to produce the printed matter. In addition, the ink jet method is preferably used as the method of applying the printing ink composition. The ink jet method is a method of ejecting fine droplets of an ink composition from an ink jet head such as an ink jet printer, and printing using this method is called ink jet printing. Hereinafter, each component contained in the treatment liquid according to the present embodiment will be described. The ink composition of the present embodiment is exemplified by an aqueous pigment ink composition used for pigment printing (printing by an ink composition using a pigment as a coloring material).

The treatment liquid according to the present embodiment is a treatment liquid for adhering to a fabric in printing, and includes: a cationic compound, betaine, and water.

[ cationic Compound ]

The cationic compound has a function of aggregating components in the ink composition. That is, when the ink composition is printed on a fabric to which the treatment liquid is applied in the production of a printed matter, the cationic compound contained in the treatment liquid promotes aggregation of particles by the action of the cationic compound with a pigment and/or resin microparticles (emulsion), and the like, thereby suppressing absorption into gaps between fibers constituting the fabric or into the fabric. This can improve the color development of the pigment in the printed matter. In addition, the cationic compound has a function of increasing the viscosity of the ink composition. This can suppress excessive permeation of the ink composition into the fabric and reduce occurrence of bleeding and color bleeding.

The function of the cationic compound is derived from the action of neutralizing the surface charge of the components contained in the ink composition or changing the pH of the ink composition. These effects can cause aggregation and precipitation of pigments and the like in the ink composition, or can increase the viscosity of the ink composition.

Examples of the cationic compound include polyvalent metal salts and cationic resins. Among them, polyvalent metal salts are preferably used from the viewpoints of improvement of color developability of pigments and suitability for cotton cloth. These cationic compounds may be used alone or in combination of two or more.

The polyvalent metal salt is a compound that contains a polyvalent metal cation of divalent or higher and an anion forming a salt with the polyvalent metal cation, and has water solubility. The polyvalent metal cation may, for example, be Ca²⁺、Cu²⁺、Ni²⁺、Mg²⁺、Zn²⁺、Ba²⁺Divalent metal ions; al (Al)³⁺、Fe³⁺、Cr³⁺And (4) trivalent metal ions are obtained. Further, the anion may, for example, be Cl^-、I^-、Br^-、SO₄ ^2-、CO₃ ^2-、ClO₃ ^-、NO₃ ^-、HCOO^-、CH₃COO^-And the like. Among such polyvalent metal salts in which polyvalent metal cations and anions are combined, calcium salts such as calcium chloride and calcium nitrate are preferably used from the viewpoint of improving the color developability by the storage stability of the treatment liquid or the expression of the aggregation action with respect to the pigment or the resin particles (emulsion). One polyvalent metal salt may be used alone or two or more kinds may be used simultaneously.

In addition to the polyvalent metal salt, a metal salt other than the polyvalent metal salt may also be used. An example of such a metal salt is a combination of Na^-、K^-Monovalent metal cations such as sodium sulfate and potassium sulfate, and anions such as those mentioned above.

Examples of the cationic resin include cationic polyurethane resins, olefin resins, and allylamine resins.

As the cationic polyurethane resin, a known resin or a commercially available product can be used. The cationic polyurethane resin may be any of a resin dissolved in a solvent such as water or an organic solvent, an emulsion resin dispersed in the above solvent, and the like. Examples of such cationic polyurethane-based resins include Hydran (registered trademark) CP-7010, 7120, 7030, 7040, 7050, 7060, 7610 (trade name, japan ink chemical industries, ltd.), Superflex (registered trademark) 600, 610, 620, 630, 640, 650 (trade name, first industrial pharmaceuticals, ltd.), and urethane emulsions WBR-2120C and 2122C (trade name, japan ink chemical industries, ltd.), and the like.

The cationic olefin resin is a polymer compound derived from an olefin monomer and having a structure such as an ethylene chain or a propylene chain as a main skeleton. The cationic olefin-based resin may be a known resin or a commercially available product, or may be any of a resin dissolved in a solvent such as water or an organic solvent, an emulsion resin dispersed in the solvent, and the like. Examples of the cationic olefin-based resin include ARROWBASE (registered trademark) CB-1200 and CD-1200 (hereinafter, referred to as tradename, Youngco).

As the cationic allylamine-based resin, known resins can be used, for example, polyallylamine hydrochloride, polyallylamine amide sulfate, allylamine hydrochloride-diallylamine hydrochloride copolymer, allylamine acetate-diallylamine acetate copolymer, allylamine hydrochloride-dimethylallylamine hydrochloride copolymer, allylamine-dimethylallylamine copolymer, polydiallylamine hydrochloride, polydiallylamine amide sulfate, polydiallylamine acetate, polydiallyldimethylammonium chloride, diallylamine acetate-sulfur dioxide copolymer, diallylmethylammonium ethylsulfate-sulfur disulfide copolymer, methyldiallylamine hydrochloride-sulfur disulfide copolymer, polyallylamine, Diallyl dimethyl ammonium chloride sulfur disulfide copolymer, diallyl dimethyl ammonium chloride acrylamide copolymer and the like.

As such cationic allylamine-based resins, commercially available products can be used, and PAA-HCL-01, 03, 05, 3L, and 10L; PAA-H-HCL; PAA-SA; PAA-01, 03, 05, 08, 15C, 25; PAA-H-10C; PAA-D11-HCL; PAA-D41-HCL; PAA-D19-HCL; PAS-21CL, 22SA, 92A; PAS-M-1, 1L, 1A; PAS-H-1L, 5L, 10L; PAS-J-81, 81L (trade name, Nittobo, Inc., Japan), Hymoloc (registered trademark) NEO-600, Q-101, Q-311, Q-501, HI-MACS SC-505 (trade name, Hymo Corp., Ltd., Japan), and the like.

In addition to the cationic resin or polyvalent metal salt, a cationic surfactant, an inorganic acid, an organic acid, or the like may be used as another cationic compound.

Examples of the cationic surfactant include primary amine, secondary amine, tertiary amine salt compounds, alkylammonium salts, dialkylammonium salts, aliphatic ammonium salts, benzalkonium salts, quaternary ammonium salts, alkylammonium salts, alkylpyridinium salts, sulfonium salts, phosphonium salts, onium salts, imidazolinium salts, and the like. Specific examples of such a cationic surfactant include: hydrochlorides or acetates of laurylamine, cocoylamine, and abietylamine; dodecyl trimethyl ammonium chloride (lauryl trimethyl ammonium chloride), hexadecyl trimethyl ammonium chloride (cetyl trimethyl ammonium chloride), benzyl tributyl ammonium chloride, benzalkonium chloride, dimethylethyl lauryl ammonium ethyl sulfate, dimethylethyl octyl ammonium ethyl sulfate, trimethyl lauryl ammonium hydrochloride, hexadecyl pyridine chloride, hexadecyl pyridine bromide, dihydroxyethyl lauryl amine, 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. Commercially available products of these cationic surfactants can be used.

The inorganic acid or organic acid may, for example, be an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid; organic acids such as 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, orthophosphoric acid, pyrrolidone carboxylic acid, pyran carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumarin acid, thiophene carboxylic acid, and nicotine acid, and derivatives or salts thereof. These may be used alone or in combination of two or more.

As other cationic compounds, it is possible to use, for example: inorganic pigments such as chalk, kaolin, calcined clay, talc, titanium oxide, zinc sulfide, synthetic silica, aluminum hydroxide, alumina, sericite, white carbon, saponite, calcium montmorillonite, sodium montmorillonite, bentonite, and the like; acrylic plastic pigments; organic pigments such as urea polymer compounds.

The content of the cationic compound contained in the treatment liquid is not particularly limited, but is preferably 0.1 mass% or more and 40 mass% or less, more preferably 2 mass% or more and 25 mass% or less, further preferably 5 mass% or more and 20 mass% or less, and particularly preferably 10 mass% or more and 20 mass% or less, with respect to the total mass of the treatment liquid. When the content of the cationic compound is in the above range, precipitation and/or separation of the cationic compound in the treatment liquid is suppressed, aggregation of the pigment and/or the resin microparticles (emulsion) in the ink composition is promoted, and absorption into the gaps or the inside of the fibers constituting the fabric is suppressed, so that the phenomenon of penetration of the color material into the back surface direction of the printing surface (strike-through) can be reduced, and the color developability of the printed matter can be improved.

[ betaine ]

Betaine refers to a compound having a positive charge and a negative charge in the same molecule and having no charge as the whole molecule. Specifically, the intramolecular salt compound may be one having a positive charge such as a quaternary ammonium cation and a negative charge such as a carboxylic acid anion at positions not adjacent to each other in the same molecule, and having no free hydrogen atom bonded to an atom having a positive charge.

Specific examples of such intramolecular salt compounds (betaines) include, but are not particularly limited to, lysine betaine, ornithine betaine, lobster myosine, trigonelline, alanine betaine, taurine betaine, phenylalanine betaine-carnitine complex, homoserine betaine, valine betaine, trimethylglycine (glycine betaine), stachydrine hydrochloride, γ -butylbetaine, lauryl dimethylaminoacetic acid betaine, lauryl hydroxysultaine, stearyl dimethylaminoacetic acid betaine, lauramidopropyl betaine, cocamidopropyl betaine, and glutamic betaine, and one or more selected from these are used. Among them, it is preferable to use one or more selected from L-carnitine, trimethylglycine and γ -butylbetaine in accordance with the trapping effect of the cationic compound. Further, commercially available products of these betaines may be used.

The trace of pretreatment is estimated to be caused by the reaction between the cationic compound in the pretreatment agent and the components contained in the fabric. In contrast, the inclusion of betaine suppresses the reaction of the cationic compound with the components contained in the fabric (cloth). This is because the cationic compound is trapped by betaine and is less likely to react with components contained in the fabric. When the cationic compound captured by betaine is subjected to printing with a color material after pretreatment, the capture of betaine is released and a reaction with the color material or the like proceeds. Therefore, color development is improved by aggregation of color materials and the like. Thus, the color developability can be ensured, and the treatment liquid composition can be provided in which the generation of pretreatment traces is suppressed as compared with the prior art. In addition, the appearance quality of the product produced by printing and dyeing can be improved.

Betaine is presumed to exist in a state where at least a certain amount of cationic compound is trapped in the treatment solution. Therefore, when the treatment liquid is attached to the fabric as pretreatment, the amount of the cationic compound that reacts with the components contained in the fabric decreases, and the occurrence of pretreatment traces is suppressed. When printing is performed using an aqueous ink composition, the cationic compound is released from the captured state due to high compatibility with the cationic compound in the aqueous ink composition, and the aggregation with a pigment or the like in the ink composition is expressed.

The content of betaine in the treatment liquid is preferably 0.2 or more by mass ratio, more preferably 0.3 or more by mass ratio, and still more preferably 0.6 or more by mass ratio with respect to the content of the cationic compound. The trapping effect of the betaine on the cationic compound can be easily expressed by setting the content of betaine to the content of the cationic compound as described above. As a result, generation of a trace of pretreatment is appropriately suppressed by the treatment liquid.

The content of betaine in the treatment liquid is preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less, in terms of a mass ratio to the content of the cationic compound. By setting the content of betaine to the content of the cationic compound as described above, it is possible to reduce the occurrence of strike-through and improve the color developability of the printed matter.

The appropriate content of betaine in the treatment liquid varies depending on the color of the fabric to be used. In the case of application to a fabric dyed black or blue, the content of betaine in the treatment liquid is preferably 1.25 to 2.0 in terms of a mass ratio to the content of the cationic compound, from the viewpoint of being able to suitably suppress the occurrence of treatment traces. In the case of application to a fabric dyed red, the content of betaine in the treatment liquid is preferably 0.6 to 1.25 in terms of a mass ratio to the content of the cationic compound, from the viewpoint of being able to suitably suppress the occurrence of treatment traces.

The content of betaine in the treatment liquid is preferably 5.0 mass% or more based on the total mass of the treatment liquid. This can further suppress the generation of a trace of pretreatment.

The content of betaine in the treatment liquid is preferably 20 mass% or less with respect to the total mass of the treatment liquid. Accordingly, the fabric exhibits appropriate wettability and permeability. Therefore, when the treatment agent is applied to the fabric, the treatment agent is easily and uniformly absorbed at an appropriate speed, and the occurrence of a difference in the amount of the treatment agent attached (uneven application) caused when the treatment agent is applied can be suppressed.

[ Water ]

Water is a main medium of the treatment liquid of the present embodiment. After the treatment liquid is attached to the fabric, water is a component evaporated by drying. As the water, for example, pure water such as ion-exchanged water, ultrafiltrated water, reverse osmosis water, and distilled water, or ultrapure water from which ionic impurities have been removed as much as possible can be used. Further, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide or the like is used, the generation of mold or bacteria can be suppressed when the treatment liquid is stored for a long period of time.

The content of water contained in the treatment liquid is not particularly limited, and is 30 mass% or more and 95 mass% or less, preferably 40 mass% or more and 90 mass% or less, more preferably 45 mass% or more and 85 mass% or less, and further preferably 50 mass% or more and 80 mass% or less with respect to the total mass of the treatment liquid. By setting the water content in the above range, the handling property of the treatment liquid when it is attached to the fabric and the drying property after attachment can be improved while suppressing an increase in the viscosity of the treatment liquid. The water in the treatment liquid also includes water used as a raw material of the treatment liquid, for example, water blended in a resin emulsion or the like described later.

[ resin emulsion ]

The treatment liquid may also contain a resin emulsion. By adding the resin emulsion, the fixability of the pigment contained in the ink composition to the fabric can be improved. Further, a resin emulsion may be used as an eye-filling agent for suppressing excessive penetration of the treatment liquid or the ink composition into the fabric.

In the case where water is used as the main medium of the treatment liquid as in the present embodiment, the resin emulsion is obtained by dispersing resin fine particles in an aqueous medium. As a method for dispersing the resin fine particles, a forced emulsification type using an emulsifier (surfactant), a self emulsification type in which a hydrophilic portion (hydrophilic group) is introduced into a molecular structure of the resin fine particles, and the like can be used. The resin fine particles may have reactivity (crosslinking reactivity), and for example, a resin having an isocyanate group masked with a blocking agent in a molecular structure may be used.

Examples of the material for forming the resin microparticles include a polyurethane resin, a vinyl acetate resin, an acrylic resin, a styrene-acrylic resin, a polyester resin, and the like, and at least one of them can be used.

The average particle diameter of the resin fine particles is preferably 30nm or more and 300nm or less, and more preferably 40nm or more and 100nm or less. When the average particle diameter is within the above range, the dispersibility of the resin emulsion in the treatment liquid and the fixability to the fabric can be improved. Here, in the present specification, unless otherwise specified, "average particle diameter" means a volume-standard particle size distribution (50%). The average particle diameter is measured by a dynamic light scattering method or a laser diffraction method described in JIS Z8825. Specifically, a particle size distribution meter (for example, "microtrack upa" manufactured by Nikkiso K.K.) using a dynamic light scattering method as a measurement principle can be used.

Commercially available products of this resin emulsion can be used. Examples of the urethane resin emulsion include Superflex (registered trademark) 150, 420, 460, 470, 500, 610, 700, 800, 870, 6E-2000, E-2500, E-4000, and R-5000 (the same applies to the first Industrial pharmaceutical Co., Ltd.); adeka Bontighter (registered trademark) HUX-290K, 380, 822 and 830 (trade names, Adeka Corp., supra); takelac (registered trademark) W-6020, 6021, 6061, 605, 635 (trade name, Mitsui chemical polyurethane Co., Ltd.); permarin (registered trademark) UA-150 (trade name, Sanyo chemical industries Co., Ltd.); sun Cure (registered trademark) 2710 (trade name, luoborun, japan); NeoRez (registered trademark) R-940, 9637, 9660 (trade name, Nanba cost chemical Co., Ltd.) and the like.

Examples of the vinyl acetate resin emulsion include Vinyblan (registered trademark) 1245L (trade name, japan chemical industry corporation); polysol (registered trademark) SH-502, AD-2, 10, 13, 17, 70, 96 (trade name, Showa Denko K.K.); seikadyne (registered trademark) 1900W (trade name, Dari Seikagan Co., Ltd.), and the like.

Examples of the acrylic resin emulsion include Voncoat (registered trademark) AN-402, R-3310, R-3360 and 4001 (trade name, DIC corporation); polysol (registered trademark) AM-710, 920, 2300, AP-4735, AT-860, PSASE-4210E (trade name, Showa Denko K.K.); saibinol (registered trademark) SK-200(SAIDEN chemical Co.); AE-120A (trade name, JSR Corp.); vinyblan (registered trademark) 2650, 2680, 2682, 2684, 2886, 5202, (trade name, japanese chemical industry corporation); NK-Binder-R-5HN (trade name, Ningzhongcun chemical industries, Ltd.), and the like.

Examples of the styrene-acrylic resin emulsion include Microgel (registered trademark) E-1002, 5002 (trade name, Nippon Paint, Inc.); voncoat (registered trademark) 5454 (trade name, DIC corporation); polysol (registered trademark) AP-7020 (trade name, showa electric corporation, supra); SAE1014 (trade name, japanese swizzein (Zeon)); AE373D (trade name, E-Tech corporation); joncryl (registered trademark) 390, 450, 511, 631, 632, 711, 734, 741, 775, 780, 790, 840, 852, 1535, 7001, 7100, 7600, 7610, 7640, 7641, 74J, 352D, 352J, 537J, 538J, HRC-1645J, PDX-7145, 7630A (above, trade name, BASF corporation); mowinyl (registered trademark) 966A, 7320 (japan synthetic chemical company), and the like.

Examples of the polyester resin emulsion include Eritel (registered trademark) KA-5071S, KT-8701, 8803, 8904, 9204, 0507 (trade name, Youngco Co., Ltd.); hightech SN-2002 (trade name, Toho chemical Co., Ltd.), and the like.

The content of the resin emulsion in terms of solid content in the treatment liquid is preferably 1 mass% or more and 20 mass% or less, more preferably 1.5 mass% or more and 15 mass% or less, and still more preferably 2 mass% or more and 10 mass% or less, based on the total mass of the treatment liquid. When the content of the resin emulsion in terms of solid content is in the above range, the increase in viscosity of the treatment liquid can be suppressed, and the wash fastness, the friction fastness, and the like in printed matter can be improved.

[ surfactant ]

The treatment solution may further contain a surfactant. The surfactant has a function of reducing the surface tension of the treatment liquid and improving the permeability to the fabric. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant, and at least one of them can be used.

The content of the surfactant when added to the treatment liquid is preferably 0.3% by mass or less based on the total mass of the treatment liquid. More preferably 0.25% by mass or less, and still more preferably 0.2% by mass or less. When the content of the surfactant is in the above range, excessive reduction in the surface tension of the treatment liquid can be suppressed, and the treatment liquid can be easily held in the vicinity of the surface of the fabric when the treatment liquid is attached to the fabric. This makes it possible to express the function of the treatment liquid easily.

As the nonionic surfactant, an acetylene glycol surfactant, a fluorine surfactant, a silicone surfactant, and the like can be used. By using these surfactants, the wettability to the fabric can be improved with a relatively small content.

The acetylene glycol surfactant is not particularly limited, and may, for example, be an alkylene oxide adduct of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, 2, 4-dimethyl-5-decyne-4-ol, an alkylene oxide adduct of 2, 4-dimethyl-5-decyne-4-ol, 3, 6-dimethyl-4-octyne-3, 6-diol, 3, 5-dimethyl-1-hexyne-3-ol, 2, 4-dimethyl-5-hexyne-3-ol, or the like.

Commercially available acetylene glycol surfactants can be used. Examples thereof include Surfynol (registered trademark) 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, and DF110D (the trade names are as described above, Air Products and Chemicals, Inc.); olfine (registered trademark) 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 (above, trade name, japanese chemical industry); acetylenol (registered trademark) E00, E00P, E40, E100 (trade name, Chuanjian Fine chemical Co., Ltd.) and the like.

As the fluorine-based surfactant, commercially available ones can be used, and examples thereof include Megaface (registered trademark) F-479 (trade name, DIC Co.); BYK-340 (trade name, BYK Corp.), and the like.

The silicone surfactant is not particularly limited, and a polysiloxane compound can be used. The polysiloxane compound is not particularly limited, and a polyether-modified organosiloxane may be mentioned. Examples of commercially available products of the polyether-modified organosiloxane may include BYK-302, 306, 307, 333, 341, 345, 346, 347, 348 (trade name, BYK), KF-351A, 352A, 353, 354L, 355A, 615A, 945, 640, 642, 643, 6020, 6011, 6012, 6015, 6017, and X-22-4515 (trade name, shin-Etsu chemical industries, Ltd.).

Examples of the anionic surfactant include higher fatty acid salts, soaps, α -sulfo fatty acid methyl ester salts, alkylbenzene sulfonates, alkyl sulfate ester salts, alkyl ether sulfate ester salts, monoalkyl phosphate ester salts, α -olefin sulfonates, alkylnaphthalene sulfonates, naphthalene sulfonates, alkane sulfonates, polyoxyethylene alkyl ether sulfates, sulfosuccinate ester salts, polyoxyalkylene glycol alkyl ether phosphate ester salts, and the like.

Examples of the cationic surfactant include quaternary ammonium salt compounds such as alkyltrimethylammonium salts, dialkyldimethylammonium salts and alkyldimethylbenzylammonium salts; amine salt compounds such as N-methyl dihydroxy ethylamine fatty acid ester hydrochloride. The cationic surfactant may be the above cationic compound.

The amphoteric surfactant is not particularly limited, but examples thereof include amino acid compounds such as alkyl amino fatty acid salts.

The surfactant may be used alone or in combination of two or more. In addition, it is preferable to use a surfactant having an HLB (hydrophilic lipophilic balance) value of 13 or more. Thus, when the treatment liquid is applied to the fabric, the penetration into the fabric and wet spreading can be controlled.

[ other ingredients ]

Various additives or organic solvents such as pH adjusters, preservatives, mildewcides, antioxidants, chelating agents, and the like may be added to the treatment liquid.

The pH adjuster is not particularly limited, and examples thereof include organic bases and inorganic bases. The organic base may, for example, be an alkanolamine such as triethanolamine, diethanolamine, monoethanolamine or triisopropanolamine. As the inorganic base, a strong base such as a hydroxide of an alkali metal or an alkaline earth metal, for example, lithium hydroxide, potassium hydroxide, or calcium hydroxide can be used.

Examples of the preservative or antifungal agent include sodium benzoate, sodium pentachlorophenol, 2-pyridinethiol-1-sodium oxide, sodium sorbate, sodium dehydroacetate, and 1, 2-dibenzothiazolin-3-one (trade names PROXEL CRL, PROXEL BDN, PROXEL GXL, PROXEL XL-2, and PROXEL TN available from Losa (LONZA)). By adding a preservative or a mildew preventive to the treatment liquid, the propagation of bacteria or molds in the treatment liquid can be suppressed.

The organic solvent may be added to adjust the physical properties of the treatment liquid such as viscosity and surface tension, the drying property of the treatment liquid, and the like. In the case of adding an organic solvent, an organic solvent for an ink composition described later can be applied.

As described above, the treatment liquid according to the present embodiment is used for adhering to a fabric serving as a base material of a printed matter in advance when the printed matter is produced by applying (printing) the ink composition, and is different from the ink composition. The content of the color material in the treatment liquid according to the present embodiment is preferably a specific value or less. Specifically, the content of the coloring material is 0.5% by mass or less, more preferably 0.1% by mass or less, still more preferably 0.05% by mass or less, and particularly preferably not contained (0% by mass), based on the total mass of the treatment liquid.

[ method for preparing treatment liquid ]

The treatment solution can be prepared by mixing the above components in an arbitrary order and, if necessary, subjecting the mixture to filtration or the like to remove impurities, or the like. As a method for mixing the respective components, a method is employed in which materials (components) are sequentially added to a vessel equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed. As a filtration method, centrifugal filtration, filter filtration, or the like can be employed.

[ Properties of treatment solution ]

The physical properties of the treatment liquid can be optionally adjusted depending on the type of fabric, the method of adhering to the fabric (coating method), and the like. The method of applying the treatment liquid will be described later.

The viscosity of the treatment liquid at 20 ℃ is not particularly limited, but is preferably 1.5 to 100 mPas (millipascal seconds), more preferably 1.5 to 50 mPas, and still more preferably 1.5 to 20 mPas. By setting the viscosity of the treatment liquid within the above range, the coating property such as the spreadability of the treatment liquid when it is attached to a fabric can be improved.

When the ink jet method is used for the coating method, the viscosity of the treatment liquid at 20 ℃ is preferably 1.5 to 15mPa · s, more preferably 1.5 to 10mPa · s, and still more preferably 1.5 to 7.0mPa · s. By setting the viscosity in the case of using the ink jet method to the above range, the stability of the treatment liquid discharged from the ink jet head can be improved, and the treatment time of the process for adhering the treatment liquid can be shortened.

The viscosity of the treatment liquid was measured, for example, using a viscoelasticity tester MCR-300 (manufactured by Pysica). Specifically, the measurement can be performed by adjusting the temperature of the treatment liquid to 20 ℃ and reading the cut viscosity (mPa · s) at a cut speed of 200 (1/s).

The surface tension of the treatment liquid at 25 ℃ is, for example, preferably 30mN/m or more and 50mN/m or less, and more preferably 35mN/m or more and 45mN/m or less. When the surface tension of the treatment liquid at 25 ℃ is in the above range, the treatment liquid exhibits appropriate wettability and permeability to the fabric, so that the treatment agent can be uniformly absorbed by the fabric at an appropriate speed when the treatment agent is applied to the fabric, and the occurrence of a difference in the amount of the treatment agent adhered (uneven application) caused when the treatment agent is applied can be suppressed.

The surface tension of the treatment liquid is measured, for example, by using an automatic surface tensiometer CBVP-Z (Kyowa interface science Co.). Specifically, the measurement can be performed by reading the surface tension when the platinum plate is wetted with the treatment solution in an environment of 25 ℃.

< ink composition >

Next, an ink composition for producing a printed matter by printing a fabric to which the treatment liquid of the present embodiment is applied will be described. As described above, the ink composition according to the present embodiment is an aqueous ink composition for textile printing, and preferably an aqueous ink composition for inkjet textile printing. Hereinafter, the components contained in the ink composition of the present embodiment will be described.

[ color material ]

The ink composition of the present embodiment uses a dye or a pigment as a coloring material. Examples of the dye include water-soluble dyes such as acid dyes and basic dyes; disperse dyes with the use of a dispersant (surfactant); reactive dyes, and the like. The dye is impregnated by forming a chemical bond between the molecules of the dye and a functional group of a fabric forming material, thereby realizing printing. Known dyes can be used as the dye.

The ink composition of the present embodiment is preferably a pigment printing ink using a pigment as a color material, from the viewpoint of simplifying the processes such as the padding process and the washing process, as compared with the case of using a dye. That is, the treatment liquid of the present embodiment is preferably used for pigment printing, and more preferably used for inkjet pigment printing.

As the pigment, any of known organic pigments and inorganic pigments can be used. The organic pigment may, for example, be an azo pigment such as an azo lake pigment, an insoluble azo pigment, a condensed azo pigment or a chelate azo pigment; polycyclic pigments such as phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, isoindoline pigments, quinophthalone pigments, and diketopyrrolopyrrole pigments; dye lake pigments such as basic dye lake and acid dye lake; nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments, and the like. Examples of the inorganic pigment include metal oxide pigments such as titanium dioxide, zinc oxide, and chromium oxide; carbon black, and the like. In addition, bright pigments such as pearl pigments and metallic pigments may be used.

Examples of such pigments include c.i. (color index common Name) pigment black 1, 7, and 11 for black pigment ink compositions. Among them, carbon black (c.i. pigment black 7) having a relatively low specific gravity and hardly sedimenting in an aqueous medium is preferable for ink jet textile printing.

Examples of the pigment for a color ink composition include c.i. pigment yellow 1,3, 12, 13, 14, 17, 24, 34, 35, 37, 42, 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 138, 153, 155, 180; c.i. pigment red 1,2, 3,5, 17, 22, 23, 31, 38, 48:2 (permanent red 2b (ba)), 48:2 (permanent red 2b (ca)), 48:3, 48:4, 49:1, 52:2, 53:1, 57:1, 60:1, 63:2, 64:1, 81, 83, 88, 101, 104, 105, 106, 108, 112, 114, 122, 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 219; c.i. pigment violet 19, 23; c.i. pigment blue 1,2, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17:1, 56, 60, 63; c.i. pigment green 1,4, 7, 8, 10, 17, 18, 36, etc. The average particle diameter of the pigment is preferably 5 μm or less, more preferably 0.3 μm or less, and still more preferably in the range of 0.01 to 0.15. mu.m. When the average particle diameter of the pigment is in the above range, the ejection stability from the inkjet head can be ensured, and the color developability of the pigment in a printed matter can be improved.

In the treatment liquid of the present embodiment, a white ink composition is preferably used in combination in order to secure the color developability of the color material. Specifically, there is a method of printing a white ink composition on a fabric colored in advance to form a base, such as a color image. This method is performed to suppress interference with the color of a fabric (color of the fabric) of a printed color image and to improve the color development of the image. That is, when the treatment liquid and the white ink composition of the present embodiment are used, the color development property of the white pigment can improve the hiding property, and an image of a desired color or the like can be printed regardless of the color of the fabric.

Examples of the white pigment for the white ink composition include c.i. pigment white 1 (basic lead carbonate), 4 (zinc oxide), 5 (a mixture of zinc sulfide and barium sulfate), 6 (titanium dioxide), 6: 1 (titanium dioxide containing another metal oxide), 7 (zinc sulfide), 18 (calcium carbonate), 19 (clay), 20 (mica titanium), 21 (barium sulfate), 22 (gypsum), 26 (magnesium oxide-silica), 27 (silica), and 28 (anhydrous calcium silicate). Among them, c.i. pigment white 6 excellent in color developability, hiding property, and the like is preferably used.

The average particle diameter of the white pigment is preferably in the range of 100 μm to 500. mu.m, more preferably 150 μm to 450 μm, and still more preferably 200 μm to 400 μm. By setting the average particle diameter of the white pigment to the above range, the ejection stability from the inkjet head can be ensured. In addition, the covering property with respect to the color dyed in advance on the fabric cloth can be improved.

In the present specification, the "average particle diameter" means a volume-standard particle size distribution (50%), if not otherwise specified. The average particle diameter of the pigment can be measured by the same method as that for the average particle diameter of the resin fine particles.

The content of the pigment in the case of using the pigment is not particularly limited, and is preferably, for example, 0.1 mass% or more and 30 mass% or less with respect to the total mass of the ink composition. More preferably 1 to 20% by mass, and still more preferably 1 to 15% by mass. When the content of the pigment is within the above range, the color developability of the pigment can be ensured and the increase in viscosity of the ink composition and the occurrence of clogging in the ink jet head can be suppressed in a printed matter subjected to printing and dyeing.

The above pigments may be used singly or in combination of two or more. In order to improve dispersibility in the ink composition, it is preferable to perform surface treatment on the pigment, or to blend a dispersant or the like in the ink composition. The surface treatment of the pigment refers to a method of introducing a hydrophilic group such as a carboxyl group or a sulfo group to the particle surface of the pigment by physical treatment or chemical treatment. The pigment can be dispersed in an aqueous medium such as water by surface treatment of the pigment.

The dispersant used for an aqueous medium has a function of adsorbing a hydrophobic portion (hydrophobic group) in a molecular structure to the particle surface of a pigment and aligning a hydrophilic portion (hydrophilic group) to the medium side. By this action, the pigment can be dispersed in an aqueous medium. As the dispersant, a known surfactant or a polymer compound is used. Further, a method of coating the pigment particles with a polymer compound or the like to impart dispersibility may be employed. As a method for covering the pigment particles, an acid precipitation method, a phase inversion emulsification method, a microemulsion polymerization method, or the like can be employed.

[ Water ]

The ink composition of the present embodiment is an aqueous pigment ink composition as described above, and water is a main medium of the ink composition of the present embodiment. When the ink composition is applied to the fabric, water evaporates from the fabric by drying. The same water as the above-mentioned treatment liquid can be used as the water. The content of water contained in the ink composition is, for example, 30 mass% to 90 mass%, preferably 40 mass% to 85 mass%, and more preferably 50 mass% to 80 mass% with respect to the total mass of the ink composition. When the content of water is within the above range, the viscosity of the ink composition can be inhibited from increasing. In the present specification, the term "aqueous ink composition" refers to an ink composition having a water content of 30% by mass or more relative to the total mass of the ink composition.

[ organic solvent ]

An organic solvent may be added to the ink composition. By adding the organic solvent, physical properties such as viscosity and surface tension, and behaviors such as drying and penetration when applied to a fabric can be adjusted. Examples of the organic solvent include 2-pyrrolidones, 1, 2-alkanediols, polyhydric alcohols, glycol ethers, and the like. These may be used singly or in combination of two or more.

The 2-pyrrolidones mean compounds having a 2-pyrrolidone skeleton. Examples of the 2-pyrrolidone include compounds having a substituent such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-vinyl-2-pyrrolidone, in addition to unsubstituted 2-pyrrolidone. The substituent in the 2-pyrrolidone skeleton is preferably an organic group such as a saturated or unsaturated hydrocarbon group having 1 to 5 carbon atoms. Among them, 2-pyrrolidone, which is excellent in the storage stability of the ink composition and the effect of suppressing the generation of aggregates, is more preferably used.

Examples of the 1, 2-alkanediols include 1, 2-propanediol, 1, 2-butanediol, 1, 2-pentanediol, 1, 2-hexanediol, and 1, 2-octanediol. The 1, 2-alkanediols are excellent in improving the wettability of an ink composition to a fabric and in wetting the fabric uniformly. Therefore, an image or the like in which the occurrence of bleeding is suppressed can be formed. The content of the 1, 2-alkanediol added is preferably 1 to 20% by mass based on the total mass of the ink composition.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 3-pentanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2, 3-butanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 2-methyl-2, 4-pentanediol, and glycerin. By adding the polyhydric alcohol to the ink composition, drying or curing of the ink composition in the discharge nozzle of the inkjet head can be suppressed, and clogging of the discharge nozzle, discharge failure, or the like can be reduced. The content of the polyhydric alcohol when added is preferably 2 to 20 mass% based on the total mass of the ink composition. In addition, the polyol which is solid at 20 ℃ also has the same action as the polyol of the organic solvent, and can be used similarly. Examples of the polyhydric alcohol which is solid at 20 ℃ include trimethylolpropane and the like.

Examples of the glycol ether include an alkylene glycol monoether and an alkylene glycol diether.

Examples of the alkylene glycol monoethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether (butyl triethylene glycol), tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

Examples of the alkylene glycol diether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether.

By adding a glycol ether to the ink composition, the wettability to the fabric and the permeation rate can be adjusted. The content of the glycol ether when added is preferably 0.05 mass% or more and 6 mass% or less with respect to the total mass of the ink composition.

The organic solvent may be used in combination of a plurality of kinds. In this case, the total content of the organic solvents in the ink composition is 0.2 mass% or more and 30 mass% or less, preferably 0.4 mass% or more and 20 mass% or less, more preferably 0.5 mass% or more and 15 mass% or less, and further preferably 0.7 mass% or more and 10 mass% or less, with respect to the total mass of the ink composition. When the total content of the organic solvent is within the above range, the increase in viscosity of the ink composition can be suppressed, the behavior (penetration and wet spreading) in the fabric can be adjusted, and the ejection failure of the inkjet head and the like can be reduced.

[ surfactant ]

A surfactant may be added to the ink composition. The surfactant has a function of reducing the surface tension of the ink composition and improving the permeability to the fabric. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant, and at least one of them can be used. The same surfactants as those used in the above-mentioned treatment liquids can be used as the surfactants.

By adding the surfactant to the ink composition, the components of the treatment liquid adhering to the fabric can be easily brought into contact while suppressing foaming and ensuring ejection stability from the inkjet head.

[ chelating agent ]

A chelating agent may be added to the ink composition. The chelating agent has a function of capturing metal ions and the like. Therefore, when the chelating agent is used in the ink composition, it is possible to capture metal ions contained in the ink composition as impurities or mixed in from a member contacting the ink composition, thereby reducing the generation of impurities derived from the metal ions. Examples of the chelating agent include Ethylenediaminetetraacetate (EDTA), nitrilotriacetate of ethylenediamine, hexametaphosphate, pyrophosphate, and metaphosphate.

[ pH adjusting agent ]

A pH adjuster may be added to the ink composition. The pH adjuster is not particularly limited, and examples thereof include organic bases and inorganic bases. The pH of the ink composition is preferably adjusted to a range of 7.5 to 10.5 using these pH adjusters. When the pH of the ink composition is in the above range, corrosion of members such as an ink repellent film can be suppressed in an ink jet textile printing apparatus including an ink jet head.

The organic base may, for example, be an alkanolamine such as triethanolamine, diethanolamine, monoethanolamine or triisopropanolamine. Here, in order to make the pH of the ink composition within the above range using these organic bases, a relatively large amount needs to be added. Specifically, the content is, for example, about 0.1 mass% or more and 3 mass% or less with respect to the total mass of the ink composition.

As the inorganic base, a strong base such as a hydroxide of an alkali metal or an alkaline earth metal, for example, lithium hydroxide, potassium hydroxide, or calcium hydroxide can be used. In order to adjust the pH of the ink composition to the above range using these inorganic bases, the content of the inorganic bases with respect to the total mass of the ink composition may be, for example, about 0.03 mass% to about 0.15 mass%. Thus, the amount of the inorganic base to be added is preferably small compared with the organic base, and the inorganic base does not have odor or the like as the organic base.

[ resin ]

A resin may be added as a fixing agent to the ink composition. By adding the resin, the washing fastness and the rubbing fastness of the printed matter can be further improved, and the fuzzing of the fabric can be suppressed. The resin may be the same resin emulsion as the treatment liquid. A water-soluble resin may be used in addition to the resin emulsion. Examples of the water-soluble resin include carboxymethyl cellulose, cellulose acetate, hydroxyethyl cellulose, and salts thereof.

The content of the resin is preferably 2 mass% or more and 25 mass% or less in terms of solid content with respect to the total mass of the ink composition. More preferably 4 to 15 mass%, and still more preferably 5 to 11 mass%. When the content ratio of the resin is within the above range, the occurrence of nozzle clogging of the head can be reduced, and the washing fastness and the rubbing fastness of the printed matter can be further improved.

[ other ingredients ]

In the ink composition, various additives such as an antioxidant, a preservative similar to the treatment liquid, and a fungicide can be used as appropriate as other components.

[ preparation of ink composition ]

The ink composition according to the present embodiment can be prepared by mixing the above components in an arbitrary order, and if necessary, filtering the mixture to remove impurities or impurities. As a method for mixing the respective components, a method is employed in which materials (components) are sequentially added to a vessel equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed. As a filtration method, centrifugal filtration, filter filtration, or the like can be employed.

[ physical Properties of ink composition ]

The viscosity of the ink composition is preferably 1.5 mPas to 15 mPas at 20 ℃. More preferably 1.5 mPas to 10 mPas, still more preferably 1.5 mPas to 7 mPas. By setting the viscosity of the ink composition within the above range, the ejection stability and ejection amount of the ink composition from the inkjet head can be ensured. In addition, in the case of a viscosity deviating from the above range, the ejection stability of the ink composition may be ensured by changing the ejection condition of the ink composition in the inkjet head or the type of the inkjet head, and for example, the ejection stability may be ensured up to 22mPa · s under the temperature adjustment condition. The viscosity of the ink composition can be measured by the same method as that for the treatment liquid.

The surface tension of the ink composition at 25 ℃ is preferably 10mN/m or more and 40mN/m or less, and more preferably 25mN/m or more and 40mN/m or less. When the surface tension of the ink composition at 25 ℃ is in the above range, the wettability to the fabric or the contact with the components of the treatment liquid attached to the fabric can be promoted when the fabric is printed. The viscosity and surface tension of the ink composition can be measured by the same method as the treatment liquid.

< ink jet textile printing apparatus >

[ Printer ]

Next, an ink jet textile printing apparatus according to the present embodiment will be described with reference to fig. 1. The ink jet textile printing apparatus is an apparatus that performs textile printing by ejecting droplets of an ink composition onto a fabric by an ink jet method in which the droplets are ejected. Fig. 1 is a schematic perspective view showing an inkjet textile printing apparatus according to an embodiment. In the present embodiment, a shelf printer in which an ink cartridge is mounted on a carriage will be described as an example of an inkjet textile printing apparatus. In fig. 1, the proportions of the respective members are different from those in reality in order to make the respective members recognizable.

The printer 1 of the present embodiment is a so-called serial printer. The serial printer is a printer that prints while mounting an inkjet head on a carriage that moves in a predetermined direction and moving the inkjet head along with the movement of the carriage.

As shown in fig. 1, the printer 1 includes an inkjet head 3, a carriage 4, a main scanning mechanism 5, a platen roller 6, and a control unit (not shown) that controls the overall operation of the printer 1. The ink cartridges 7a, 7b, 7c, 7d, 7e, and 7f for containing the ink composition supplied to the ink jet head 3 are detachable from the carriage 4 while the carriage 4 is loaded with the ink jet head 3.

The main scanning mechanism 5 includes a timing belt 8 connected to the carriage 4, a motor 9 for driving the timing belt 8, and a guide shaft 10. The guide shaft 10 is a support member for the carriage 4 and extends in the scanning direction (main scanning direction) of the carriage 4. The carriage 4 is driven by a motor 9 via a timing belt 8 and can move back and forth along a guide shaft 10. Thus, the main scanning mechanism 5 has a function of moving the carriage 4 back and forth in the main scanning direction.

The platen roller 6 has a function of conveying the fabric 2 to be subjected to printing in a sub-scanning direction (a longitudinal direction of the fabric 2) perpendicular to the main scanning direction. Therefore, the fabric 2 is conveyed in the sub-scanning direction. The carriage 4 on which the ink jet head 3 is mounted is movable back and forth in the main scanning direction that coincides with the width direction of the fabric 2, and the ink jet head 3 is capable of relatively scanning the fabric 2 in the main scanning direction and the sub-scanning direction.

The ink cartridges 7a, 7b, 7c, 7d, 7e, 7f are independent 6 ink cartridges. The ink cartridges 7a, 7b, 7c, 7d, 7e, and 7f can contain the ink composition of the present embodiment. The ink cartridges individually contain ink compositions of colors such as black, cyan, magenta, yellow, white, orange, and the like, and can be used in any combination. In fig. 1, the number of ink cartridges is 6, but is not limited thereto. Supply ports (not shown in the drawings) for supplying the ink compositions contained in the respective ink cartridges to the ink-jet head 3 are provided in the bottom portions of the ink cartridges 7a, 7b, 7c, 7d, 7e, 7 f.

The ink jet head 3 has a nozzle surface (not shown) on a surface facing the fabric 2. On the nozzle surface, nozzle rows (not shown) each including a plurality of nozzles (not shown) are provided corresponding to the respective color ink compositions. The ink compositions of the respective colors are supplied from the respective ink cartridges to the inkjet head 3, and are ejected as droplets from the nozzles by actuators (not shown in the drawings) in the inkjet head 3. The discharged droplets of the ink composition are ejected onto the fabric 2, and an image, text, a pattern, a color, and the like are formed on the printed region of the fabric 2.

Here, the inkjet head 3 uses a piezoelectric element as an actuator (driving mechanism), but is not limited to this type. For example, an electromechanical conversion element that displaces a vibrating plate as an actuator by electrostatic attraction, or an electrothermal conversion element that ejects an ink composition as droplets by bubbles generated by heating may be used.

In the present embodiment, the on carriage printer 1 is used as an example of the inkjet textile printing apparatus, but the present invention is not limited thereto. For example, an off carriage printer may be used in which an ink composition container such as an ink cartridge is not mounted on a carriage. The ink jet textile printing apparatus used in the present invention is not limited to the above-described serial printer, and may be a line head printer in which an ink jet head is formed to be wide and wider than or equal to the width of the fabric 2, and the textile printing is performed without moving the ink jet head.

[ Fabric ]

The fabric 2 according to the present embodiment may be in the form of a raw fabric, a garment, or another clothing article. The grey cloth includes woven, knitted, non-woven fabric, etc. Clothing and other accessories include furniture such as T-shirts, handkerchiefs, scarves, towels, handbags, cloth bags, curtains, sheets, bedspreads, and wallpaper after sewing, and also includes fabric before and after cutting as a part before sewing. Examples of such forms include a long form wound in a roll form, a form cut into a predetermined size, and a form of a product shape. The fabric 2 may be coated with the treatment liquid of the present embodiment, and a material to which the treatment liquid is applied in advance may be used as the fabric 2.

Examples of the material for forming the fabric 2 include natural fibers such as cotton, silk, hemp, and wool; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, polyurethane, and polylactic acid, and blended fibers thereof may be used.

The fabric 2 has a basis weight of 1.0oz (ounce) to 10.0oz, preferably 2.0oz to 9.0oz, more preferably 3.0oz to 8.0oz, and even more preferably 4.0oz to 7.0 oz. In the treatment liquid of the present embodiment, since the components of the treatment liquid such as the cationic compound are appropriately arranged with respect to the fabric 2 having the basis weight in the above range, the color developability can be improved as compared with the conventional art. In addition, the fabric can be used for a plurality of kinds of fabrics having different basis weights.

As the fabric 2, a cotton fabric colored with a dye in advance is preferably used. The treatment liquid of the present embodiment can suppress the occurrence of a trace of pretreatment while ensuring color developability, and is preferably used for clothes and other accessories, such as cotton T-shirts colored in advance. That is, even in the case of a colored fabric, since the color developability is good and printing in which the occurrence of a pretreatment mark is suppressed can be realized, the quality of a printed matter as a product and the commercial value are improved as compared with the conventional art.

Examples of the dye for coloring the fabric 2 in advance include water-soluble dyes such as acid dyes and basic dyes; disperse dyes with the use of a dispersant (surfactant); reactive dyes, and the like. In the case of a cotton fabric using the fabric 2, a reactive dye suitable for dyeing cotton is preferably used.

As the reactive dye, a triazine compound having a triazine structure in the molecule is preferably used. In particular, in plant fibers such as cotton, the state of exhaust dyeing is stabilized by a reactive dye having a triazine structure. On the other hand, the triazine compound may react with a cationic compound such as a polyvalent metal ion to become one of the factors of the trace of the pretreatment. In particular, in a cotton fabric densely dyed with black or red, the occurrence of pretreatment marks tends to be remarkable.

The treatment liquid of the present embodiment has an effect of suppressing the trace of pretreatment, and thus can be suitably used for a fabric dyed with a reactive dye having a triazine structure. That is, it is preferable that the fabric 2 contains the triazine compound by dyeing with a reactive dye having a triazine structure.

Among the disperse dyes having a triazine structure, monochlorotriazine dyes which are more stable in the exhaust state are more preferably used. As the monochlorotriazine dye, there are no particular limitations, and c.i. reactive blue 15, 15:1, 49; c.i. reactive red 3, 3:1, 24, 31; c.i. reactive yellow 2, 95; c.i. reactive black 8, 39; c.i. reactive oranges 12, 13; c.i. active violet 1, etc., at least 1 selected from these groups can be used.

The reactive dye is not particularly limited except for the dyes mentioned above, and examples thereof include c.i. reactive blue 2,3, 5, 7, 13, 14, 21, 25, 26, 38, 39, 40, 41, 46, 50, 69, 72, 109, 120, 143, 176; c.i. reactive red 2,4,7, 12, 13, 14, 15, 16, 29, 32, 33, 43, 45, 46, 55, 58, 59, 79, 106, 111, 124, 218; c.i. reactive yellow 3,6, 7, 12, 15, 18, 22, 37, 42, 57, 69, 76, 81, 86, 102, 125, 135, 181; c.i. reactive black 1,3, 4, 5, 10, 12, 13, 14, 31, 34, 35; huntsman Black (hensmei Black); c.i. reactive orange 2, 5, 20, 99; c.i. active violet 1,2, 33; c.i. reactive green 5, 8; c.i. reactive brown 1,2, 7, 8, 9, 11, 14, etc., at least 1 selected from these groups can be used.

As a method for coloring the fabric 2 with a dye, a known method can be employed depending on the material, form, and the like of the fabric 2.

< ink jet textile printing method >

Next, the ink jet textile printing method according to the present embodiment will be described. The ink jet textile printing method according to the present embodiment is a method of printing by ejecting droplets of an ink composition by an ink jet method using the printer 1 (see fig. 1) and applying the droplets to a fabric 2 to form an image or the like.

The inkjet textile printing method according to the present embodiment includes a step S1 of applying the treatment liquid according to the present embodiment to the fabric 2. Further, the method includes step S3 of adhering the pigment printing ink as the ink composition to the area of the fabric 2 to which the treatment liquid is adhered by an ink jet method.

In step S1, the treatment liquid according to the present embodiment is applied to at least a part of the region of the fabric 2. Examples of the coating method for applying the treatment liquid to the fabric 2 include a method of immersing the fabric 2 in the treatment liquid (dip coating), a method of applying the treatment liquid using a brush, a roll, a doctor blade, a roll coater, or the like (roll coating), a method of spraying the treatment liquid using a spray device, or the like (spray coating), and a method of spraying the treatment liquid using an inkjet method (inkjet coating), and any coating method may be adopted depending on the form of the fabric 2, the physical properties of the treatment liquid, or the like, and a plurality of methods may be used in combination. Among the above coating methods, dip coating, roll coating, spray coating, and the like, which are simple in apparatus configuration and can rapidly impart a treatment liquid, are preferable.

In the step S1, the amount of the treatment liquid adhering to the fabric 2 is preferably 100mg/inch per unit area of the fabric 2²Above 3000mg/inch²Hereinafter, more preferably 130mg/inch²Above 15000mg/inch²More preferably 193mg/inch²Above 500mg/inch²The following. The amount of the treatment solution adhering to the surface of the substrate was set to 0.02g/cm²(129mg/inch²) As described above, the treatment liquid adheres relatively uniformly to the fabric 2, and the occurrence of color unevenness and the like can be reduced when the pigment printing ink is printed in a subsequent process. Further, the amount of the treatment liquid deposited was set to 0.5g/cm²(3226mg/inch²) Hereinafter, the occurrence of bleeding can be reduced when printing a pigment printing ink.

In step S1, the amount of adhesion of the cationic compound contained in the treatment liquid to the fabric 2 is preferably 7.5. mu. mol/cm per unit area of the fabric 2²Above 40 mu mol/cm²Hereinafter, more preferably 12. mu. mol/cm²Above 30 mu mol/cm²The following. By setting the amount of the cationic compound to be deposited to 10. mu. mol/cm²As described above, the color developability of the pigment is improved when the pigment printing ink is printed in a subsequent process. Further, the amount of the cationic compound deposited was set to 40. mu. mol/cm²Hereinafter, the washing fastness of the printed matter is improved.

The ink jet textile printing method according to the present embodiment may further include a step S2 of drying the treatment liquid applied to the fabric 2 after the step S1. For the drying of the treatment liquid, natural drying or drying by heating (heat drying) is used. It is preferable to use heat drying which can shorten the drying time. The heating method in the heat drying is not particularly limited, and examples thereof include a hot press method, an atmospheric steam method, a high pressure steam method, and a thermosetting method. The heat source for heating is not particularly limited, and for example, an infrared lamp or the like can be used.

The heating temperature in the thermal drying is preferably a temperature at which the resin fine particles (emulsion) contained in the treatment liquid exhibit an adhesive force based on the anchor effect to the fabric fibers due to a decrease in melt viscosity caused by heating in addition to volatilization of the solvent such as moisture contained in the treatment liquid. Specifically, it is not particularly limited, but is 100 ℃ or higher and 200 ℃ or lower. The heating temperature in the present process is the surface temperature of the treatment liquid adhering to the fabric 2, and can be measured by, for example, a non-contact thermometer IT2-80 (trade name, manufactured by KEYENCE corporation). The heating time for heating is not particularly limited, and is, for example, 30 seconds to 20 minutes.

Since the treatment liquid of the present embodiment contains betaine, the cationic compound is captured by betaine. Therefore, in the processes S1 and S2, even if the treatment liquid comes into contact with the fabric 2, the cationic compound is less likely to react with the components contained in the fabric 2, and the occurrence of the treatment traces is suppressed.

In step S3, the droplets of the pigment printing ink discharged from the ink jet head 3 (see fig. 1) are caused to land on the fabric 2 in the region where at least a part of the treatment liquid adheres, as described above. At this time, components such as the pigment contained in the pigment printing ink react with the cationic compound released from the trapping of betaine, and the components such as the pigment aggregate in the vicinity of the surface of the fabric 2. Therefore, the pigment is less likely to intrude into the inside of the fabric 2, and the color developability of the pigment is improved as compared with the case where the cationic compound is not used.

By using the ink jet method as the printing method, a plate or the like required for simulation printing such as screen printing is not required, and it becomes easy to cope with a large variety of small-volume production and highly fine images, texts, patterns, colors, and the like can be formed.

In the step S3, the amount of the pigment printing ink adhering to the fabric 2 is preferably 1.5mg/cm per unit area of the fabric 2²Above and 6mg/cm²Hereinafter, more preferably 2mg/cm²Above and 5mg/cm²The following. When the amount of the pigment printing ink to be attached is within the above range, the color development of an image or the like formed by printing is improved, the drying property of the pigment printing ink to be attached to the fabric 2 is secured, and the occurrence of bleeding of the image or the like is reduced. In addition, relative toIn the case where the base is formed of the white ink composition or the like, the white ink composition is preferably adhered to the colored fabric in an amount exceeding the above-mentioned adhering amount.

As a process subsequent to the process S3, a process S4 of heating the pigment printing ink attached to the fabric 2 may be provided. The process S4 can employ the same heating method as the above-described process S2. When the pigment printing ink contains a resin, the heating temperature may be set so that the resin is fused and a medium such as moisture is volatilized. Specifically, it is not particularly limited, but is 100 ℃ or higher and 200 ℃ or lower. Here, the heating temperature in the present process means a surface temperature of an image or the like formed on the fabric 2. The heating temperature can be measured by the same method as in the above-described process S2. The time for heating is not particularly limited, and is, for example, 30 seconds to 20 minutes.

After the process S4, a process S5 of washing and drying the fabric 2 subjected to the printing may be provided. In the water washing, components such as pigment printing ink not fixed to the fabric 2 may be washed with hot soap solution or the like as soaping treatment, if necessary. The printed matter is manufactured by the above process.

In the present embodiment, the application of the treatment liquid (step S1) and the printing (step S3) are performed as continuous steps, but the present invention is not limited thereto. For example, if the treatment liquid of the present invention is applied to the fabric 2 to carry out the pretreatment, the treatment liquid may be stored, transported, or the like during a period before the fabric 2 is used for printing.

As described above, according to the treatment liquid and the ink jet textile printing method according to the present embodiment, the following effects can be obtained.

According to the treatment liquid of the present embodiment, the occurrence of a trace of pretreatment can be suppressed in the fabric 2 to which the treatment liquid has been adhered. Specifically, the inclusion of betaine suppresses the reaction between a cationic compound such as a polyvalent metal ion and the components contained in the fabric 2. This is because the cationic compound is captured by betaine and hardly reacts with the components contained in the fabric 2. When the dye is printed with a color material after the pretreatment, the cationic compound captured by betaine is released from the state of being captured by betaine, and the reaction with a pigment or the like proceeds. Therefore, color development is improved by aggregation of the pigment or the like. Thus, the color developability can be ensured, and the treatment liquid in which the generation of the trace of the pretreatment is suppressed as compared with the conventional art can be provided. In addition, the appearance quality of a product (printed matter) produced by printing can be improved.

By using a pigment for a color material to perform pigment printing, the color developability of the color material can be further improved. In addition, the process such as the dip dyeing process or the cleaning process can be simplified as compared with the dye. Further, the type of fibers that can be used is relatively less limited than when using dyes, and printing can be performed on a wide variety of fibers.

By using a cotton fabric colored with a dye as the fabric 2, the occurrence of a trace of pretreatment is suppressed while ensuring color developability. Thus, a cotton fabric such as a T-shirt colored in advance can be suitably used for clothing or other accessories. That is, even if the fabric is colored, since printing can be performed with good color development and with the occurrence of the pretreatment traces suppressed, the quality and commercial value of the printed matter as a product can be improved as compared with the conventional art.

By using a triazine compound such as a reactive dye for coloring the fabric 2, the state of padding can be stabilized in a plant fiber such as cotton. In addition, even when the triazine compound is used, since the treatment liquid contains betaine, the reaction of the triazine structure with the cationic compound is suppressed, and the generation of a trace of pretreatment can be suppressed.

By using a calcium salt of a polyvalent metal salt as the cationic compound, the occurrence of a trace of pretreatment is further suppressed, and the color developability of the pigment is further improved and the pigment can be used more suitably for cotton cloth and the like.

When the treatment liquid is attached to the fabric 2, the penetration and wet spreading with respect to the fabric 2 can be controlled by containing the surfactant having an HLB value of 13 or more. In addition, when the content of the surfactant is 0.3% by mass or less based on the total mass of the treatment liquid, excessive reduction in the surface tension of the treatment liquid is suppressed, and the treatment liquid is easily held in the vicinity of the surface of the fabric when attached to the fabric. This makes it possible to express the function of the treatment liquid easily.

According to the ink jet textile printing method of the present embodiment, it is possible to provide an ink jet textile printing method in which occurrence of a trace of pretreatment is suppressed as compared with the conventional art while color developability is ensured.

By using the ink jet method, a plate or the like required for the analog printing is not required, and it becomes easy to cope with a large variety of small-volume production and it is possible to form a highly fine image or the like.

When used for printing, the fabric 2 can ensure color development and can suppress the occurrence of pretreatment marks compared with the conventional fabric. That is, the appearance quality of the product produced by printing can be improved.

Hereinafter, the treatment liquid of the present embodiment will be described in more detail by showing examples and comparative examples in which the trace of pretreatment and the color developability of a color material are evaluated.

< preparation of treating liquid >

The compositions of the treatment solutions of examples 1 to 44 and comparative examples 1 to 5 are shown in tables 1,2 and 3. In tables 1 to 3, the numerical values in the tables are expressed in units of mass%, and the content ratio of the effective ingredient (solid component) is expressed in addition to the polyvalent metal salt, l-carnitine, trimethylglycine, γ -butylbetaine, and nonionic surfactant. And ion-exchanged water was adjusted and added so that the total mass of the treatment liquid reached 100.0 mass%. The column marked "-" in which no numerical value is described in the table means not contained.

Here, in the treatment liquid of example 1, 16.0 mass% of calcium nitrate tetrahydrate as a polyvalent metal salt (cationic compound) and 12.8 mass% of l-carnitine as betaine were used. Mowinyl (registered trademark) 966A (japan synthetic chemical company) 2.7 mass% of styrene-acrylic resin was used as a resin emulsion. And Surfynol (registered trademark) 485 (trade name, air and chemical products, HLB value 17) using an acetylene glycol-based surfactant was used as a nonionic surfactant in an amount of 0.2 mass%.