Inkjet printing method and ink set

Abstract

To provide an inkjet printing method which has good friction fastness of an obtained image.SOLUTION: An inkjet printing method includes a reaction liquid adhesion step of discharging a reaction liquid containing a coagulant and water by an inkjet method, and attaching the reaction liquid to a fabric, and a color ink adhesion step of discharging color ink containing a pigment, water and a resin aggregated by the coagulant by an inkjet method, and attaching the color ink to the fabric, wherein at least one of the reaction liquid and the color ink contains a crosslinking agent, a coating amount of the pigment is 0.12 mg / inch2 or more, and a coating amount of a crosslinkable functional group is 0.05 mol / kg or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an inkjet textile printing method and an ink set. [Background technology]

[0002] The inkjet method is not only used to record images on paper, etc., but also to print fabrics, and various inkjet printing methods have been studied. Inkjet inks for printing contain coloring materials, such as dyes and pigments, to obtain images of desired colors. In addition, many studies have been conducted on inks and recording methods for inkjet printing.

[0003] For example, Patent Document 1 describes a recording method that includes a pretreatment liquid application step and an ink application step, and the ink contains a crosslinking agent. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-090617 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the recording method described in Patent Document 1, the ink contains a crosslinking agent, and the abrasion resistance of the resulting image is not necessarily sufficient. [Means for solving the problem]

[0006] One aspect of the inkjet printing method according to the present invention comprises: a reaction liquid deposition step of ejecting a reaction liquid containing a flocculant and water by an inkjet method and depositing the reaction liquid on the fabric; a colored ink applying step of ejecting a colored ink containing a pigment, water, and a resin that aggregates with the aggregating agent by an inkjet method and applying the ink to the fabric; and At least one of the reaction liquid and the colored ink contains a crosslinking agent; The coating amount of the pigment is 0.12 mg / inch 2 That's all, The amount of crosslinkable functional group applied is 0.05 mol / kg or more.

[0007] One aspect of the ink set according to the present invention is a reaction liquid containing a flocculant and water; a colored ink containing a pigment, water, and a resin that aggregates with the aid of the aggregating agent; a transparent ink containing water and a resin that aggregates with the aid of the aggregating agent; Including, at least two of the reaction liquid, the colored ink, and the transparent ink contain a crosslinking agent; The coating amount of the pigment is 0.12 mg / inch 2 That's all, The composition is applied by being ejected by an ink jet method so that the amount of crosslinkable functional group applied is 0.05 mol / kg or more, and is then attached to the fabric. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram showing the overall configuration of a printing apparatus that can be used with a printing method according to an embodiment of the present invention. [Figure 2] Table 1 shows the compositions and evaluation results of the examples. [Figure 3] Table 2 shows the compositions and evaluation results of the examples. [Figure 4] Table 3 shows the compositions and evaluation results of comparative examples and reference examples. DETAILED DESCRIPTION OF THE INVENTION

[0009] The following describes embodiments of the present invention. The embodiments described below are examples of the present invention. The present invention is not limited to the following embodiments, and includes various modified forms that are implemented within the scope of the present invention. Note that not all of the configurations described below are necessarily essential configurations of the present invention.

[0010] 1. Inkjet printing method The inkjet printing method according to this embodiment includes a reaction liquid applying step of ejecting a reaction liquid containing a flocculant and water by an inkjet method and allowing the reaction liquid to adhere to a fabric, and a colored ink applying step of ejecting a colored ink containing a pigment, water, and a resin that aggregates with the flocculant by an inkjet method and allowing the colored ink to adhere to the fabric.

[0011] 1.1.Fabric The inkjet printing method of this embodiment forms an image on a fabric.

[0012] The fabric is not particularly limited. The material constituting the fabric is not particularly limited, and examples thereof include natural fibers such as cotton, linen, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane; and biodegradable fibers such as polylactic acid, and blended fibers thereof are also acceptable. The fabric may be any of the above-mentioned fibers in the form of woven fabric, knitted fabric, nonwoven fabric, etc., or may be a blended fabric.

[0013] The fabric may be any of the above fibers in the form of woven fabric, knitted fabric, nonwoven fabric, etc. The basis weight of the fabric used in this embodiment is not particularly limited, and may be 1.0 oz or more and 10.0 oz or less, preferably 2.0 oz or more and 9.0 oz or less, more preferably 3.0 oz or more and 8.0 oz or less, and even more preferably 4.0 oz or more and 7.0 oz or less. If the basis weight of the fabric is within this range, good recording can be performed.

[0014] In this embodiment, examples of the form of the fabric include cloth, clothing, and other accessories. Fabrics include woven fabrics, knitted fabrics, nonwoven fabrics, and the like. Clothing and other accessories include sewn T-shirts, handkerchiefs, scarves, towels, carrier bags, cloth bags, curtains, sheets, bedspreads, wallpaper, and other furniture, as well as fabrics before and after cutting as parts before sewing. These forms include long rolls, cut to a predetermined size, and finished products.

[0015] The fabric may be a cotton fabric that has been pre-colored with a dye. Examples of dyes that can be used to pre-color a fabric include water-soluble dyes such as acid dyes and basic dyes, disperse dyes that are used in combination with a dispersant, and reactive dyes. The fabric may not contain a flocculant. Even with such fabric, an image with good abrasion fastness can be obtained by the inkjet printing method of this embodiment.

[0016] It is more preferable to use a fabric containing cotton, since when the fabric contains cotton, a reaction with the crosslinking agent described below can be expected, and the adhesion between the fabric and the recording layer is improved, thereby more significantly improving the effect of improving the resistance to friction.

[0017] 1.2. Reaction solution attachment process In the reaction liquid application step, a reaction liquid containing a flocculant and water is ejected by an ink jet method and applied to the fabric.

[0018] 1.2.1.Reaction solution The reaction liquid contains at least a flocculant and water.

[0019] 1.2.1.(1) Flocculant The aggregating agent has the effect of aggregating pigments and resin particles by reacting with components such as pigments contained in the ink and resin particles that may be contained in the ink, etc. Such aggregation can, for example, enhance the color development of the pigment, improve the fixation of the resin particles, and / or increase the viscosity of the ink, etc.

[0020] The flocculant is not particularly limited, but examples thereof include metal salts, inorganic acids, organic acids, cationic compounds, etc., and examples of the cationic compounds that can be used include cationic resins (cationic polymers), cationic surfactants, etc. Among these, polyvalent metal salts are preferred as metal salts, and cationic resins are preferred as cationic compounds. Therefore, it is preferred that the flocculant be selected from cationic resins, organic acids, and polyvalent metal salts, as this will result in particularly excellent image quality, abrasion resistance, gloss, etc.

[0021] The metal salt is preferably a polyvalent metal salt, but metal salts other than polyvalent metal salts can also be used. Among these flocculants, it is preferable to use at least one selected from metal salts and organic acids because of their excellent reactivity with the components contained in the ink. Furthermore, among cationic compounds, it is preferable to use cationic resins because they are easily soluble in the softening liquid. Furthermore, it is also possible to use multiple types of flocculants in combination.

[0022] Polyvalent metal salts are compounds composed of divalent or higher metal ions and anions. Examples of divalent or higher metal ions include calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, and iron ions. Among the metal ions that compose these polyvalent metal salts, at least one of calcium ions and magnesium ions is preferred because they have excellent coagulation properties for ink components.

[0023] The anions constituting the polyvalent metal salt are inorganic or organic ions. That is, the polyvalent metal salt in the present invention is composed of an inorganic or organic ion and a polyvalent metal. Examples of such inorganic ions include chloride ions, bromide ions, iodide ions, nitrate ions, sulfate ions, and hydroxide ions. Examples of organic ions include organic acid ions, such as carboxylate ions.

[0024] The polyvalent metal compound is preferably an ionic polyvalent metal salt, and in particular, when the polyvalent metal salt is a magnesium salt or a calcium salt, the stability of the softening liquid is improved. The counter ion of the polyvalent metal may be either an inorganic acid ion or an organic acid ion.

[0025] Specific examples of the polyvalent metal salt include calcium carbonate, such as heavy calcium carbonate and light calcium carbonate, calcium nitrate, calcium chloride, calcium sulfate, magnesium sulfate, calcium hydroxide, magnesium chloride, magnesium carbonate, barium sulfate, barium chloride, zinc carbonate, zinc sulfide, aluminum silicate, calcium silicate, magnesium silicate, copper nitrate, calcium formate, calcium acetate, magnesium acetate, and aluminum acetate. These polyvalent metal salts may be used alone or in combination. Among these, calcium formate, magnesium sulfate, calcium nitrate, and / or calcium chloride are preferred because they can ensure sufficient solubility in water and reduce traces left by the fabric softener (making the traces less noticeable), with calcium formate and calcium nitrate being more preferred. These metal salts may contain water of hydration in their raw material form.

[0026] Examples of metal salts other than polyvalent metal salts include monovalent metal salts such as sodium salts and potassium salts, such as sodium sulfate and potassium sulfate.

[0027] Suitable examples of organic acids include poly(meth)acrylic 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, pyrrolidonecarboxylic acid, pyronecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, pyridinecarboxylic acid, coumaric acid, thiophenecarboxylic acid, nicotinic acid, or derivatives of these compounds, or salts thereof. One organic acid may be used alone, or two or more organic acids may be used in combination. Metal salts of organic acids are included in the above-mentioned metal salts.

[0028] Examples of inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc. The inorganic acids may be used alone or in combination of two or more.

[0029] Examples of cationic resins (cationic polymers) include cationic urethane resins, cationic olefin resins, cationic amine resins, cationic surfactants, etc. The cationic polymer is preferably water-soluble.

[0030] As the cationic urethane resin, commercially available products can be used, such as Hydran CP-7010, CP-7020, CP-7030, CP-7040, CP-7050, CP-7060, and CP-7610 (trade names, manufactured by Dainippon Ink and Chemicals, Inc.), Superflex 420, 420NS, 600, 610, 620, 630, 640, and 650 (trade names, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and Urethane Emulsion WBR-2120C and WBR-2122C (trade names, manufactured by Taisei Fine Chemical Co., Ltd.).

[0031] The cationic olefin resin has an olefin such as ethylene or propylene in its structural skeleton, and known resins can be appropriately selected and used. The cationic olefin resin may also be in an emulsion state dispersed in a solvent containing water or an organic solvent. Commercially available cationic olefin resins can be used, such as Arrowbase CB-1200 and CD-1200 (trade names, manufactured by Unitika Ltd.).

[0032] The cationic amine resin (cationic polymer) may be any resin having an amino group in its structure, and known resins may be appropriately selected and used. Examples include polyamine resins, polyamide resins, and polyallylamine resins. Polyamine resins are resins having amino groups in their main skeletons. Polyamide resins are resins having amide groups in their main skeletons. Polyallylamine resins are resins having a structure derived from allyl groups in their main skeletons.

[0033] Examples of cationic polyamine resins include Unisense KHE103L (hexamethylenediamine / epichlorohydrin resin, 1% aqueous solution with a pH of approximately 5.0, a viscosity of 20 to 50 (mPa·s), and a solids concentration of 50% by mass) and Unisense KHE104L (dimethylamine / epichlorohydrin resin, 1% aqueous solution with a pH of approximately 7.0, a viscosity of 1 to 10 (mPa·s), and a solids concentration of 20% by mass), both manufactured by Senka Corporation. Specific examples of commercially available cationic polyamine resins include FL-14 (manufactured by SNF Co., Ltd.), Arafix 100, 251S, 255, and 255LOX (manufactured by Arakawa Chemical Co., Ltd.), DK-6810, 6853, and 6885; WS-4010, 4011, 4020, 4024, 4027, and 4030 (manufactured by Seiko PMC Co., Ltd.), and Papiogen P-105 (manufactured by Senka Co., Ltd.). , Sumirez Resin 650 (30), 675A, 6615, SLX-1 (manufactured by Taoka Chemical Co., Ltd.), Catiomaster (registered trademark) PD-1, 7, 30, A, PDT-2, PE-10, PE-30, DT-EH, EPA-SK01, TMHMDA-E (manufactured by Yokkaichi Synthetic Co., Ltd.), Jetfix 36N, 38A, 5052 (manufactured by Satoda Chemical Co., Ltd.).

[0034] Examples of polyamine resins include polyallylamine resins. Examples of polyallylamine resins include polyallylamine hydrochloride, polyallylamine amidosulfate, allylamine hydrochloride-diallylamine hydrochloride copolymer, allylamine acetate-diallylamine acetate copolymer, allylamine acetate-diallylamine acetate copolymer, allylamine hydrochloride-dimethylallylamine hydrochloride copolymer, allylamine-dimethylallylamine copolymer, polydiallylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldiallylamine amidosulfate, polymethyldiallylamine acetate, polydiallyldimethylammonium chloride, diallylamine acetate-sulfur dioxide copolymer, diallylmethylethylammonium ethyl sulfate-sulfur dioxide copolymer, methyldiallylamine hydrochloride-sulfur dioxide copolymer, diallyldimethylammonium chloride-sulfur dioxide copolymer, and diallyldimethylammonium chloride-acrylamide copolymer.

[0035] Examples of cationic surfactants include primary, secondary, and tertiary amine salt compounds, alkylamine salts, dialkylamine salts, aliphatic amine salts, benzalkonium salts, quaternary ammonium salts, quaternary alkylammonium salts, alkylpyridinium salts, sulfonium salts, phosphonium salts, onium salts, and imidazolinium salts.

[0036] A plurality of types of these flocculants may be used. Furthermore, if at least one of polyvalent metal salts, organic acids, and cationic resins is selected from these flocculants, the flocculating action is more favorable, and therefore images of higher quality (especially with better color development) can be formed.

[0037] The total content of the flocculant in the reaction liquid composition is not limited, but is, for example, 0.1% by mass or more and 15% by mass or less, preferably 1% by mass or more and 10% by mass or less, and more preferably 2% by mass or more and 10% by mass or less, relative to the total mass of the reaction liquid composition.

[0038] 1.2.1.(2) Water The reaction liquid contains water. The reaction liquid is an aqueous composition. "Aqueous" means that it contains at least water as a solvent component, and may contain water as a main solvent component.

[0039] Examples of water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as ultrapure water with reduced ionic impurities. Furthermore, using water that has been sterilized by ultraviolet irradiation or the addition of hydrogen peroxide can suppress the growth of bacteria and fungi when the clear ink composition is stored for a long period of time.

[0040] The content of water in the liquid medium component is preferably 50% by mass or more, and more preferably 50 to 100% by mass. Furthermore, it is preferably 70 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 99% by mass. The liquid medium is a solvent component such as water or an organic solvent.

[0041] The water content is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more, relative to the total mass of the reaction solution. The upper limit of the water content is not particularly limited, but is, for example, preferably 99% by mass or less, and even more preferably 95% by mass or less, relative to the total mass of the reaction solution.

[0042] 1.2.1.(3) Crosslinking Agent The reaction liquid may contain a crosslinking agent, such as a blocked isocyanate or an oxazoline group-containing polymer.

[0043] A blocked isocyanate compound is a chemically protected isocyanate compound that contains latent isocyanate groups whose isocyanate groups are protected by a blocking agent.

[0044] The blocked isocyanate compound can be obtained, for example, by reacting a polyisocyanate compound with a blocking agent. By including such a blocked isocyanate, crosslinking of the ink composition is less likely to proceed during storage, and after printing, the isocyanate group is deprotected by heating, crosslinking occurs, and excellent abrasion resistance is obtained. The isocyanate group protected by the protecting group is deprotected and activated by the application of heat, forming a chemical bond such as a urethane bond, urea bond, allophanate bond, biuret bond, or isocyanurate bond.

[0045] The polyisocyanate compound used in the production of the blocked isocyanate compound is not particularly limited, but examples thereof include polyisocyanate monomers and polyisocyanate derivatives.

[0046] The polyisocyanate monomer is not particularly limited, but examples thereof include polyisocyanates having an aromatic ring, aliphatic polyisocyanates, and alicyclic polyisocyanates. These polyisocyanate monomers may be used alone or in combination of two or more.

[0047] Examples of the polyisocyanate having an aromatic ring include, but are not limited to, tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate. Examples of the aliphatic polyisocyanate include, but are not limited to, hexamethylene diisocyanate. Examples of the alicyclic polyisocyanate include, but are not limited to, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.

[0048] Examples of the polyisocyanate derivatives include polymers of the above-mentioned polyisocyanate monomers (for example, dimers, trimers (for example, isocyanurate-modified products, iminooxadiazinedione-modified products), pentamers, heptamers, etc.), allophanate-modified products (for example, allophanate-modified products produced by the reaction of the above-mentioned polyisocyanate monomers with low-molecular-weight polyols described below), polyol-modified products (for example, polyol-modified products (alcohol adducts) produced by the reaction of polyisocyanate monomers with low-molecular-weight polyols described below), and biuret-modified products (for example, , biuret modified products produced by the reaction of the above-mentioned polyisocyanate monomer with water or amines), urea modified products (for example, urea modified products produced by the reaction of the above-mentioned polyisocyanate monomer with diamine), oxadiazinetrione modified products (for example, oxadiazinetrione produced by the reaction of the above-mentioned polyisocyanate monomer with carbon dioxide), carbodiimide modified products (for example, carbodiimide modified products produced by the decarboxylation condensation reaction of the above-mentioned polyisocyanate monomer), uretdione modified products, uretonimine modified products, etc.

[0049] When two or more types of polyisocyanate compounds are used in combination, for example, when producing a blocked isocyanate compound, two or more types of polyisocyanate compounds may be reacted simultaneously, or blocked isocyanates obtained by using each polyisocyanate compound individually may be mixed.

[0050] Blocking agents block and inactivate isocyanate groups, while deblocking them to regenerate or activate them. Examples of blocking agents include, but are not limited to, imidazole compounds, imidazoline compounds, pyrimidine compounds, guanidine compounds, alcohol compounds, phenolic compounds, active methylene compounds, amine compounds, imine compounds, oxime compounds, carbamic acid compounds, urea compounds, acid amide (lactam) compounds, acid imide compounds, triazole compounds, pyrazole compounds, mercaptan compounds, bisulfites, benzoxazolone, isatoic anhydride, and tetrabutylphosphonium acetate.

[0051] The imidazole compound is not particularly limited, but examples thereof include imidazole (dissociation temperature 100°C), benzimidazole (dissociation temperature 120°C), 2-methylimidazole (dissociation temperature 70°C), 4-methylimidazole (dissociation temperature 100°C), 2-ethylimidazole (dissociation temperature 70°C), 2-isopropylimidazole, 2,4-dimethylimidazole, and 2-ethyl-4-methylimidazole.

[0052] The imidazoline compound is not particularly limited, but examples thereof include 2-methylimidazoline (dissociation temperature 110° C.) and 2-phenylimidazoline.

[0053] The pyrimidine compound is not particularly limited, but an example thereof is 2-methyl-1,4,5,6-tetrahydropyrimidine.

[0054] The guanidine compound is not particularly limited, but examples thereof include guanidine, 3,3-dialkylguanidines such as 3,3-dimethylguanidine, 1,1,3,3-tetraalkylguanidines such as 1,1,3,3-tetramethylguanidine (dissociation temperature 120°C), and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0055] The alcohol-based compound is not particularly limited, but examples thereof include methanol, ethanol, 2-propanol, n-butanol, s-butanol, 2-ethylhexyl alcohol, 1- or 2-octanol, cyclohexyl alcohol, ethylene glycol, benzyl alcohol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2-(hydroxymethyl)furan, 2-methoxyethanol, and methoxypropanol. , 2-ethoxyethanol, n-propoxyethanol, 2-butoxyethanol, 2-ethoxyethoxyethanol, 2-ethoxybutoxyethanol, butoxyethoxyethanol, 2-butoxyethylethanol, 2-butoxyethoxyethanol, N,N-dibutyl-2-hydroxyacetamide, N-hydroxysuccinimide, N-morpholineethanol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 3-oxazolidineethanol, 2-hydroxymethylpyridine (dissociation temperature 140°C), furfuryl alcohol, 12-hydroxystearic acid, triphenylsilanol, and 2-hydroxyethyl methacrylate.

[0056] The phenolic compound is not particularly limited, and examples thereof include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, n-nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-sec-butylphenol, di-tert-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, Examples of such phenolic compounds include di-n-nonylphenol, nitrophenol, bromophenol, chlorophenol, fluorophenol, dimethylphenol, styrenated phenol, methyl salicylate, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-ethylhexyl hydroxybenzoate, 4-[(dimethylamino)methyl]phenol, 4-[(dimethylamino)methyl]nonylphenol, bis(4-hydroxyphenyl)acetic acid, 2-hydroxypyridine (dissociation temperature 80°C), 2- or 8-hydroxyquinoline, 2-chloro-3-pyridinol, and pyridine-2-thiol (dissociation temperature 70°C).

[0057] Examples of active methylene compounds include, but are not limited to, Meldrum's acid, malonic acid diesters, acetoacetic acid esters, 2-acetoacetoxyethyl methacrylate, acetylacetone, and cyanoacetic acid esters. Examples of malonic acid diesters include, but are not limited to, dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-tert-butyl malonate, di-2-ethylhexyl malonate, methyl n-butyl malonate, ethyl n-butyl malonate, methyl sec-butyl malonate, ethyl sec-butyl malonate, methyl tert-butyl malonate, ethyl tert-butyl malonate, diethyl methylmalonate, dibenzyl malonate, diphenyl malonate, benzylmethyl malonate, ethylphenyl malonate, tert-butylphenyl malonate, and isopropylidene malonate. The acetoacetate ester is not particularly limited, but examples thereof include methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, t-butyl acetoacetate, benzyl acetoacetate, and phenyl acetoacetate.

[0058] The amine compound is not particularly limited, but examples thereof include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis(2,2,6,6-tetramethylpiperidinyl)amine, di-n-propylamine, diisopropylamine (dissociation temperature 130°C), isopropylethylamine, 2,2,4- or 2,2,5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine (dissociation temperature 140°C), dicyclohexylamine (dissociation temperature 130°C), bis(3,5,5-trimethylcyclohexylamine), (hexyl)amine, piperidine, 2,6-dimethylpiperidine (dissociation temperature 130°C), tert-butylmethylamine, tert-butylethylamine (dissociation temperature 120°C), tert-butylpropylamine, tert-butylbutylamine, tert-butylbenzylamine (dissociation temperature 120°C), tert-butylphenylamine, 2,2,6-trimethylpiperidine, 2,2,6,6-tetramethylpiperidine (dissociation temperature 80°C), (dimethylamino)-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl methyl-4-piperidine, 6-methyl-2-piperidine, and 6-aminocaproic acid.

[0059] The imine compound is not particularly limited, but examples thereof include ethyleneimine, polyethyleneimine, and 1,4,5,6-tetrahydropyrimidine.

[0060] The oxime compound is not particularly limited, but examples thereof include formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime (dissociation temperature 130°C), cyclohexanone oxime, diacetyl monooxime, benzophenone oxime, 2,2,6,6-tetramethylcyclohexanone oxime, diisopropyl ketone oxime, methyl tert-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethylpentyl ketone oxime, methyl 3-ethylheptyl ketone oxime, methyl isoamyl ketone oxime, n-amyl ketone oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monooxime, 4,4'-dimethoxybenzophenone oxime, and 2-heptanone oxime.

[0061] The carbamic acid compound is not particularly limited, but an example thereof is N-phenylcarbamate phenyl.

[0062] The urea-based compound is not particularly limited, but examples thereof include urea, thiourea, and ethyleneurea.

[0063] The acid amide (lactam) compound is not particularly limited, but examples thereof include acetanilide, N-methylacetamide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5-piperazinedione, and laurolactam.

[0064] The acid imide compound is not particularly limited, but examples thereof include succinimide, maleimide, and phthalimide.

[0065] The triazole-based compound is not particularly limited, but examples thereof include 1,2,4-triazole and benzotriazole.

[0066] The pyrazole-based compound is not particularly limited, but examples thereof include pyrazole, 3,5-dimethylpyrazole (dissociation temperature 120°C), 3,5-diisopropylpyrazole, 3,5-diphenylpyrazole, 3,5-di-tert-butylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3-methyl-5-phenylpyrazole.

[0067] The mercaptan compound is not particularly limited, but examples thereof include butyl mercaptan, dodecyl mercaptan, and hexyl mercaptan.

[0068] The bisulfite is not particularly limited, but examples thereof include sodium bisulfite.

[0069] These blocking agents may be used alone or in combination of two or more. Note that for some of the compounds exemplified above, the dissociation temperature is also listed as the temperature at which the isocyanate group is regenerated.

[0070] The dissociation temperature of the blocking agent is preferably 60° C. or higher and 230° C. or lower, more preferably 80° C. or higher and 200° C. or lower, even more preferably 100° C. or higher and 180° C. or lower, and even more preferably 110° C. or higher and 160° C. If the dissociation temperature is within this range, the storage stability of the ink composition can be further improved, and furthermore, the temperature in the heating step can be set low.

[0071] Commercially available blocked isocyanates include, but are not limited to, "Takenate WB-3021" (product name, manufactured by Mitsui Chemicals, Inc.), "Elastron" series "BN-69" and "11" (all product names, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Meikanate TP-10, Meikanate NS-1, Meikanate CX, "SU-268A," "NBP-8730," and "NBP-211" (all product names, manufactured by Meisei Chemical Industry Co., Ltd.), and Trixene AQUA BI220 (product name, manufactured by GSI Creos Co., Ltd.). These blocked isocyanates may be used alone or in combination of two or more.

[0072] When a blocked isocyanate is contained, the content of the blocked isocyanate is from 0.1 to 5% by mass, more preferably from 0.5 to 4% by mass, even more preferably from 1 to 3% by mass, and still more preferably from 1.5 to 2.5% by mass. When the content of the blocked isocyanate is within this range, the rub fastness of the printed textile can be improved.

[0073] Examples of oxazoline group-containing polymers include polymers having multiple oxazoline groups bonded to the polymer main chain. Such polymers can undergo crosslinking reactions through the reaction of the oxazoline groups. Examples of oxazoline group-containing polymers include the Epocross series (manufactured by Nippon Shokubai Co., Ltd.), and among these, the emulsion-type K-2000 series is a preferred example.

[0074] When the reaction liquid contains a blocked isocyanate, a crosslinked structure can be formed in the image, resulting in an image with even better fastness.

[0075] When the reaction solution contains a crosslinking agent, it is more preferable that the crosslinking agent is cationic or nonionic. In this way, even if the reaction solution contains an aggregating agent, the crosslinking agent in the reaction solution is cationic or nonionic, so that aggregation of the crosslinking agent in the reaction solution is suppressed, thereby improving storage stability.

[0076] 1.2.1.(4) Other ingredients The reaction liquid may contain an organic solvent, a surfactant, an additive, and other components.

[0077] (organic solvent) The reaction liquid used in the recording method according to this embodiment may contain an organic solvent. The organic solvent is preferably water-soluble. One of the functions of the organic solvent is to improve the wettability of the reaction liquid to the fabric and to increase the moisture retention of the reaction liquid. The organic solvent can also function as a penetrant.

[0078] Examples of organic solvents include esters, alkylene glycol ethers, cyclic esters, nitrogen-containing solvents, polyhydric alcohols, etc. Examples of nitrogen-containing solvents include cyclic amides and non-cyclic amides, etc. Examples of non-cyclic amides include alkoxyalkylamides.

[0079] Examples of the esters include glycol monoacetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate, and glycol diesters such as ethylene glycol diacetate, diethylene glycol diacetate, and propylene glycol diacetate.

[0080] The alkylene glycol ether may be a monoether or diether of alkylene glycol, and is preferably an alkyl ether. Specific examples include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether, and alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.

[0081] Examples of cyclic esters include cyclic esters (lactones) such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and β-butyrolactone, as well as compounds in which the hydrogen atom of the methylene group adjacent to the carbonyl group of these cyclic esters is substituted with an alkyl group having 1 to 4 carbon atoms.

[0082] Examples of alkoxyalkylamides include 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-diethylpropionamide, 3-methoxy-N,N-methylethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-diethylpropionamide, 3-ethoxy-N,N-methylethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-diethylpropionamide, and 3-n-butoxy-N,N-methylethylpropionamide.

[0083] Examples of cyclic amides include lactams, such as pyrrolidones such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone.

[0084] It is also preferable to use a compound represented by the following general formula (1) as the alkoxyalkylamide.

[0085] R 1 -O-CH2CH2-(C=O)-NR 2 R 3 ···(1)

[0086] In the above formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 and R 3 each independently represents a methyl group or an ethyl group. The "alkyl group having 1 to 4 carbon atoms" can be a linear or branched alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, or a tert-butyl group. The compound represented by the above formula (1) may be used alone or in combination of two or more types.

[0087] The content of the nitrogen-containing solvent is not particularly limited, but is about 5% by mass to 50% by mass, and preferably 10% by mass to 30% by mass, based on the total mass of the reaction liquid. When the content is within the above range, the fixability and surface dryness of the image (particularly the surface dryness when recorded in a hot and humid environment) can be further improved in some cases.

[0088] Examples of polyhydric alcohols include 1,2-alkanediols (e.g., alkanediols such as ethylene glycol, propylene glycol (also known as propane-1,2-diol), 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, and 1,2-octanediol), and polyhydric alcohols (polyols) other than 1,2-alkanediols (e.g., diethylene glycol, dipropylene glycol, 1,3-propanediol, and 1,3-butanediol (also known as 1,3-butylene glycol)). glycol), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol, 2-methylpentane-2,4-diol, trimethylolpropane, glycerin, etc.

[0089] Examples of polyhydric alcohols include alkanediols and polyols. Alkanediols are diols of alkanes having 5 or more carbon atoms. The number of carbon atoms in the alkanes is preferably 5 to 15, more preferably 6 to 10, and even more preferably 6 to 8. 1,2-alkanediols are preferred.

[0090] The polyols are polyols of alkanes having 4 or less carbon atoms, or intermolecular condensation products of hydroxyl groups of polyols of alkanes having 4 or less carbon atoms. The number of carbon atoms of the alkane is preferably 2 to 3. The number of hydroxyl groups in the polyol molecule is 2 or more, preferably 5 or less, and more preferably 3 or less. When the polyol is the above-mentioned intermolecular condensation product, the number of intermolecular condensation groups is 2 or more, preferably 4 or less, and more preferably 3 or less. The polyhydric alcohols can be used alone or in combination of two or more.

[0091] Alkanediols and polyols can function primarily as penetrating solvents and / or moisturizing solvents, but alkanediols tend to have stronger penetrating solvent properties, while polyols tend to have stronger moisturizing solvent properties.

[0092] When the reaction liquid contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The total content of the organic solvent relative to the total mass of the reaction liquid is, for example, 5% by mass to 50% by mass, preferably 10% by mass to 45% by mass, more preferably 15% by mass to 40% by mass, and even more preferably 20% by mass to 40% by mass. When the content of the organic solvent is within the above range, the balance between the wetting and spreading properties and the drying properties is better, and it is easier to form a higher quality image.

[0093] The organic solvent preferably contains a polyhydric alcohol, more preferably a polyhydric alcohol having a standard boiling point of 250°C or higher. The content of the polyhydric alcohol having a standard boiling point of 250°C or higher is preferably 1% by mass or higher, more preferably 5% by mass or higher, even more preferably 10% by mass or higher, even more preferably 13% by mass or higher, and particularly preferably 15% by mass or higher, relative to the total amount of the reaction solution. There is no particular upper limit, but it is preferably 40% by mass or lower, more preferably 35% by mass or lower, even more preferably 30% by mass or lower, even more preferably 25% by mass or lower, and particularly preferably 20% by mass or lower. When the content of the polyhydric alcohol having a standard boiling point of 250°C or higher is within the above range, an excellent balance between moisture retention and drying properties tends to be achieved, and both intermittent printing stability and rub fastness tend to be good.

[0094] (surfactant) The reaction liquid may contain a surfactant. The surfactant adjusts the surface tension of the reaction liquid and functions to adjust, for example, the wettability with the fabric. Among surfactants, for example, acetylene glycol surfactants, silicone surfactants, and fluorine surfactants can be preferably used.

[0095] The acetylene glycol surfactant is not particularly limited, but examples thereof include 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, and DF110D (all trade names, manufactured by Air Products & Chemicals Co.). , Olfine 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, manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0096] The silicone surfactant is not particularly limited, but a polysiloxane compound is preferred. The polysiloxane compound is not particularly limited, but for example, a polyether-modified organosiloxane is exemplified. Commercially available products of the polyether-modified organosiloxane include, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (all trade names, manufactured by BYK-Chemie Japan), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF- 615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Silface SAG002, 005, 503A, 008 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0097] As the fluorine-based surfactant, it is preferable to use a fluorine-modified polymer, and specific examples include BYK-3440 (manufactured by BYK Japan), Surflon S-241, S-242, S-243 (all trade names, manufactured by AGC Seimi Chemical Co., Ltd.), and Futergent 215M (manufactured by Neos Corporation).

[0098] When a surfactant is contained in the reaction liquid, multiple types may be contained. When a surfactant is contained in the reaction liquid, the content of the surfactant can be 0.1% by mass or more and 2% by mass or less, preferably 0.4% by mass or more and 1.5% by mass or less, and more preferably 0.5% by mass or more and 1.0% by mass or less, based on the total mass of the reaction liquid.

[0099] (wax) The reaction liquid may contain wax, which has the function of providing lubricity to the image formed by the reaction liquid, thereby reducing peeling of the image.

[0100] Examples of wax components include plant and animal waxes such as carnauba wax, candelilla wax, beeswax, rice wax, and lanolin; petroleum waxes such as paraffin wax, microcrystalline wax, polyethylene wax, oxidized polyethylene wax, and petrolatum; mineral waxes such as montan wax and ozokerite; synthetic waxes such as carbon wax, Hoechst wax, polyolefin wax, and stearic acid amide; and natural and synthetic wax emulsions and blended waxes such as α-olefin-maleic anhydride copolymers, which can be used alone or in combination. Among these, polyolefin waxes (particularly polyethylene wax and polypropylene wax) and paraffin wax are preferred from the viewpoint of their superior effect of improving adhesion to flexible packaging films, as described below.

[0101] As the wax, commercially available products can be used as they are, such as Nopcoat PEM-17 (trade name, manufactured by San Nopco Ltd.), Chemipearl W4005 (trade name, manufactured by Mitsui Chemicals, Inc.), and AQUACER 515, 539, and 593 (all trade names, manufactured by BYK Japan K.K.).

[0102] The wax may be supplied in the form of an emulsion or suspension. When using a wax, its content is 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, and even more preferably 0.5% by mass to 2% by mass, calculated as solid content, relative to the total mass of the reaction solution. When the wax content is within the above range, the wax can exhibit its functions well.

[0103] (additives) The reaction solution may contain, as additives, ureas, amines, sugars, etc. Examples of ureas include urea, ethyleneurea, tetramethylurea, thiourea, 1,3-dimethyl-2-imidazolidinone, etc., and betaines (trimethylglycine, triethylglycine, tripropylglycine, triisopropylglycine, N,N,N-trimethylalanine, N,N,N-triethylalanine, N,N,N-triisopropylalanine, N,N,N-trimethylmethylalanine, carnitine, acetylcarnitine, etc.).

[0104] Examples of amines include diethanolamine, triethanolamine, triisopropanolamine, etc. Ureas and amines may function as pH adjusters. Examples of sugars include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose.

[0105] (pH adjuster) A pH adjuster can be added to the reaction solution of this embodiment for the purpose of adjusting the pH. The pH adjuster is not particularly limited, and examples thereof include appropriate combinations of acids, bases, weak acids, and weak bases. Examples of acids and bases used in such combinations include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid; inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium carbonate, sodium carbonate, sodium bicarbonate, and ammonia; organic bases such as triethanolamine, diethanolamine, monoethanolamine, tripropanolamine, triisopropanolamine, diisopropanolamine, and trishydroxymethylaminomethane (THAM); and organic acids such as adipic acid, citric acid, succinic acid, lactic acid, and N,N-bis(2-hydroxybenzoate). Other buffers that may be used include Good's buffers such as N-(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), morpholinoethanesulfonic acid (MES), carbamoylmethyliminobisacetic acid (ADA), piperazine-1,4-bis(2-ethanesulfonic acid) (PIPES), N-(2-acetamido)-2-aminoethanesulfonic acid (ACES), cholamine hydrochloride, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid (TES), acetamidoglycine, tricine, glycinamide, and bicine, as well as phosphate buffer, citrate buffer, and Tris buffer. Furthermore, among these, it is preferable that the pH adjuster contains, as part or all of a tertiary amine such as triethanolamine or triisopropanolamine, or a carboxyl group-containing organic acid such as adipic acid, citric acid, succinic acid or lactic acid, since this makes it possible to obtain a more stable pH buffering effect.

[0106] (Ureas) Ureas may be used as moisturizing agents for the reaction liquid. Specific examples of ureas include urea, ethylene urea, tetramethyl urea, thiourea, 1,3-dimethyl-2-imidazolidinone, etc. When ureas are contained, the content thereof can be 1% by mass or more and 10% by mass or less relative to the total mass of the reaction liquid.

[0107] (Sugars) Sugars may be used to prevent the reaction solution from solidifying or drying. Specific examples of sugars include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose.

[0108] (chelating agent) A chelating agent may be used in the reaction solution, such as ethylenediaminetetraacetic acid and salts thereof (disodium dihydrogen ethylenediaminetetraacetate, or nitrilotriacetate, hexametaphosphate, pyrophosphate, or metaphosphate of ethylenediamine).

[0109] (preservatives, anti-mold agents) The reaction solution may contain an antiseptic or an antifungal agent, such as sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel IB, and Proxel TN (all trade names manufactured by Lonza Japan), and 4-chloro-3-methylphenol (such as Preventol CMK manufactured by Bayer).

[0110] (rust inhibitor) The reaction solution may contain a rust inhibitor. Preferred examples of the rust inhibitor include benzotriazole, acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite. Among these, benzotriazole is particularly preferred.

[0111] (others) The reaction liquid used in the inkjet printing method according to this embodiment may further contain components such as a viscosity adjuster, an antioxidant, an antifungal agent, an oxygen absorber, and a dissolution aid, as necessary.

[0112] 1.2.1.(5) Physical properties and preparation of reaction solution The reaction liquid is applied to the fabric by an inkjet method, and the viscosity of the reaction liquid is preferably 1.5 mPa·s or more and 15 mPa·s or less, more preferably 1.5 mPa·s or more and 7 mPa·s or less, and even more preferably 1.5 mPa·s or more and 5.5 mPa·s or less at 20° C. When the reaction liquid is applied to the fabric by an inkjet method, it is easy to efficiently form a predetermined image on the fabric.

[0113] To ensure proper wetting and spreading of the reaction liquid onto fabric, the surface tension at 25° C. is 40 mN / m or less, preferably 38 mN / m or less, and more preferably 35 mN / m or less. The surface tension is preferably 20 mN / m or more, and more preferably 25 mN / m or more.

[0114] The surface tension can be measured by using an automatic surface tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) to check the surface tension when a platinum plate is wetted with the composition in an environment of 25°C.

[0115] The reaction solution can be obtained by mixing the above-mentioned components in any order and, if necessary, removing impurities by filtration or the like. A suitable method for mixing the components is to sequentially add the materials to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stir and mix them. As a filtration method, centrifugal filtration, filter filtration, etc. can be used as necessary.

[0116] 1.2.2. Method of applying the reaction solution to fabric The reaction liquid deposition step may be performed by any method according to the inkjet method in which the reaction liquid is deposited while scanning the inkjet head over the fabric. The inkjet method performs a main scan in which the inkjet head is moved in a direction perpendicular to the transport direction of the fabric to perform recording. It is more preferable that the reaction liquid and the colored ink are deposited on the same scanned area of ​​the fabric by the same main scan.

[0117] In the reaction solution attachment step, the amount of polyvalent metal salt in the reaction solution attached to the fabric was 0.3 (mg / inch 2 ) or more, and 2 ) or more is more preferable, and 0.9 (mg / inch 2 By setting the deposition amount to this level, even when colored inks or the like are deposited on the same scanned area of ​​the fabric by the same main scan, the components of the inks (for example, colored inks and clear inks) can be favorably aggregated, which can suppress strike-through and improve color development.

[0118] On the other hand, the adhesion amount of polyvalent metal salts was 1.7 (mg / inch 2 ) or less, and 1.5 (mg / inch 2 ) or less, and more preferably 1.0 (mg / inch 2 ) or less. This makes it possible to further improve the color development of the image.

[0119] The amount of reaction solution adhered in the reaction solution adhesion step was 5.0 (mg / inch 2 ) or more is preferable. 2 ) or more is preferable, and 9.0 (mg / inch 2 ) or more, and 10.0 (mg / inch 2 ) or more, and 12.0 (mg / inch 2 ) or more is more preferable, and 15.0 (mg / inch 2) or more. In this way, an image with even better color development can be obtained.

[0120] The upper limit is 25.0 (mg / inch 2 ) or less is preferable, and 18.0 (mg / inch 2 ) or less is more preferable, and 15.0 (mg / inch 2 ) The following is even more preferred.

[0121] The above-mentioned amount of reaction liquid adhered is the amount in the recording region where the reaction liquid and the colored ink are adhered in an overlapping manner in the inkjet printing method of this embodiment. It is also possible and preferred that the maximum amount of reaction liquid adhered in this region be within the above-mentioned range.

[0122] 1.3.Colored ink application process The inkjet printing method of this embodiment includes a colored ink application step. The colored ink application step is a step of ejecting a colored ink containing a pigment, water, and a resin that aggregates with the aggregating agent by an inkjet method and applying it to the fabric. The colored ink will be described below. The method of applying the colored ink to the fabric will be described later.

[0123] 1.3.1.Colored ink The colored ink contains at least a pigment, water, and a resin that aggregates in the presence of the above-mentioned aggregating agent.

[0124] 1.3.1.(1) Pigments The colored ink is a so-called color ink that contains a pigment. Examples of the pigment contained in the colored ink include color pigments such as cyan, yellow, magenta, black, red, green, and orange, and special color pigments such as white.

[0125] The pigment may be a mixture. The pigment has excellent storage stability such as light resistance, weather resistance, and gas resistance, and from this viewpoint, it is preferable that the pigment is an organic pigment.

[0126] Specifically, examples of pigments that can be used include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments; polycyclic pigments such as phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments; dye chelates, dye lakes, nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments, and carbon black. These pigments can be used alone or in combination of two or more. Furthermore, white pigments, luster pigments, and the like can also be used.

[0127] Specific examples of pigments include, but are not limited to, the following:

[0128] Examples of black pigments include No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, and No. 2200B (all manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, and Raven 700 (all manufactured by Carbon Columbia), Rega1 400R, Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, and Monarch 1400 (manufactured by CABOT JAPAN). KK), Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black 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 (all manufactured by Degussa), and BONJET Black CW-1, CW-2, CW-3 (manufactured by Orient Chemical Industries Co., Ltd.).

[0129] Examples of yellow pigments include CI 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, and 180.

[0130] Examples of magenta pigments include CI 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, and 245, and CI Pigment Violet. Examples include 19, 23, 32, 33, 36, 38, 43, and 50.

[0131] Examples of cyan pigments include CI Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:34, 15:4, 16, 18, 22, 25, 60, 65, and 66, and CI Vat Blue 4 and 60.

[0132] Furthermore, pigments other than magenta, cyan, and yellow are not particularly limited, but examples thereof include CI Pigment Green 7, 10, CI Pigment Brown 3, 5, 25, 26, and CI Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, and 63.

[0133] Examples of white pigments include metal oxides, barium sulfate, calcium carbonate, and other metal compounds. Examples of metal oxides include titanium dioxide, zinc oxide, silica, alumina, magnesium oxide, and the like. Furthermore, particles having a hollow structure may be used as the white pigment, and known particles having a hollow structure may be used.

[0134] It is preferable that the pigment can be stably dispersed in the dispersion medium, and therefore a dispersant may be used for dispersion. Examples of dispersants include resin dispersants, and these are selected from those that can improve the dispersion stability of the pigment in the colored ink. Furthermore, the pigment may be used as a self-dispersing pigment by modifying the surface of the pigment particles by oxidizing or sulfonating the pigment surface with, for example, ozone, hypochlorous acid, fuming sulfuric acid, or the like.

[0135] Examples of resin dispersants (dispersant resins) include (meth)acrylic resins and salts thereof such as poly(meth)acrylic acid, (meth)acrylic acid-acrylonitrile copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, vinyl acetate-(meth)acrylic acid ester copolymer, vinyl acetate-(meth)acrylic acid copolymer, and vinylnaphthalene-(meth)acrylic acid copolymer; styrene-(meth)acrylic acid copolymer, styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-α-methylstyrene-(meth)acrylic acid copolymer, and styrene-α-methylstyrene-(meth)acrylic acid copolymer. Examples of suitable water-soluble resins include styrene-based resins such as acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, and styrene-maleic anhydride copolymers, and salts thereof; urethane-based resins and salts thereof, which are polymeric compounds (resins) containing urethane bonds formed by the reaction of an isocyanate group and a hydroxyl group and may be linear and / or branched, and may have a crosslinked structure; polyvinyl alcohols; vinyl naphthalene-maleic acid copolymers and salts thereof; vinyl acetate-maleic acid ester copolymers and salts thereof; and vinyl acetate-crotonic acid copolymers and salts thereof. Among these, preferred are copolymers of a monomer having a hydrophobic functional group and a monomer having a hydrophilic functional group, and polymers composed of a monomer having both a hydrophobic and a hydrophilic functional group. The copolymers may be random copolymers, block copolymers, alternating copolymers, or graft copolymers.

[0136] Commercially available styrene resin dispersants include, for example, X-200, X-1, X-205, X-220, and X-228 (manufactured by Seiko PMC Co., Ltd.), Nopcosperse (registered trademark) 6100 and 6110 (manufactured by San Nopco Ltd.), Joncryl 67, 586, 611, 678, 680, 682, and 819 (manufactured by BASF), DISPERBYK-190 (manufactured by BYK Japan KK), N-EA137, N-EA157, N-EA167, N-EA177, N-EA197D, N-EA207D, and E-EN10 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0137] Commercially available acrylic resin dispersants include BYK-187, BYK-190, BYK-191, BYK-194N, and BYK-199 (manufactured by BYK-Chemie Co., Ltd.), Aron A-210, A6114, AS-1100, AS-1800, A-30SL, A-7250, and CL-2 (manufactured by Toagosei Co., Ltd.).

[0138] Furthermore, commercially available urethane resin dispersants include BYK-182, BYK-183, BYK-184, and BYK-185 (manufactured by BYK-Chemie Co., Ltd.), TEGO Disperse 710 (manufactured by Evonic Tego Chemi), and Borchi (registered trademark) Gen 1350 (manufactured by OMG Borschers).

[0139] The dispersants may be used alone or in combination of two or more. The total content of the dispersants is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, even more preferably 1 to 20 parts by mass, and even more preferably 1.5 to 15 parts by mass, per 50 parts by mass of the pigment. By using a dispersant content of 0.1 parts by mass or more per 50 parts by mass of the pigment, the dispersion stability of the pigment can be further improved. Furthermore, by using a dispersant content of 30 parts by mass or less per 50 parts by mass of the pigment, the viscosity of the resulting dispersion can be kept low.

[0140] Among the dispersants listed above, at least one selected from anionic dispersant resins is more preferred. In this case, the weight-average molecular weight of the dispersant is more preferably 500 or more. Furthermore, it is more preferably 5,000 or more and 100,000 or less, and even more preferably 10,000 or more and 50,000 or less.

[0141] By using such a resin dispersant as a dispersant, the dispersion and aggregation properties of the pigment are improved, and it is possible to obtain better dispersion stability and images with better image quality.

[0142] Anionic dispersant resins are resins that have anionic functional groups and exhibit anionic properties. Examples of the anionic functional groups include carboxyl groups, sulfo groups, and phosphate groups. Among these groups, carboxyl groups are more preferred.

[0143] The dispersant resin preferably has an acid value of 5 mgKOH / g or more, more preferably 10 to 200 mgKOH / g, even more preferably 15 to 150 mgKOH / g, still more preferably 20 to 100 mgKOH / g, and even more preferably 25 to 70 mgKOH / g.

[0144] The acid value can be measured by neutralization potentiometric titration in accordance with JIS K 0070. As a titration device, for example, "AT610" manufactured by Kyoto Electronics Manufacturing Co., Ltd. can be used.

[0145] The pigment content is preferably 0.3% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, even more preferably 1% by mass to 10% by mass, and even more preferably 2% by mass to 7% by mass, relative to the total mass of the colored ink.

[0146] The volume average particle size of the pigment particles is preferably 10 nm to 300 nm, more preferably 30 nm to 250 nm, even more preferably 50 nm to 250 nm, particularly preferably 70 nm to 200 nm, and even more preferably 80 nm to 150 nm.

[0147] 1.3.1.(2) Resin The colored ink contains a resin that aggregates with the aid of an aggregating agent. The resin contained in the colored ink is preferably resin particles. The colored ink may be a colored water-based resin ink. The resin particles can further improve the adhesion of an image formed by the colored ink adhered to a fabric. Examples of resin particles include anionic resin particles made of urethane-based resins, acrylic-based resins (including styrene-acrylic resins), fluorene-based resins, polyolefin-based resins, rosin-modified resins, terpene-based resins, polyester-based resins, polyamide-based resins, epoxy-based resins, vinyl chloride-based resins, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate-based resins, etc. Among these, urethane-based resins, acrylic-based resins, polyolefin-based resins, and polyester-based resins are preferred. These resin particles are often handled in the form of an emulsion, but may also be in the form of a powder. Furthermore, the resin particles can be used alone or in combination of two or more types.

[0148] Among these, the resin particles are preferably urethane resin, since the selection of urethane resin allows the formation of images with even better resistance to friction.

[0149] Urethane resin is a general term for resins having urethane bonds. In addition to urethane bonds, the urethane resin may be a polyether urethane resin containing ether bonds in the main chain, a polyester urethane resin containing ester bonds in the main chain, or a polycarbonate urethane resin containing carbonate bonds in the main chain. Furthermore, commercially available products may be used as the urethane resin. For example, commercially available products such as Superflex 420NS, 460, 460s, 840, and E-4000 (trade names, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Rezamin D-1060, D-2020, D-4080, D-4200, D-6300, and D-6455 (trade names, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.), Takelac WS-6021 and W-512-A-6 (trade names, manufactured by Mitsui Chemicals Polyurethanes Inc.), Sancure 2710 (trade name, manufactured by LUBRIZOL), Permarin UA-150 (trade name, manufactured by Sanyo Chemical Industries, Ltd.), and the ETANACOL UW series, such as UW-1527 (manufactured by Ube Industries, Ltd.), may be used.

[0150] Acrylic resin is a general term for polymers obtained by polymerizing at least an acrylic monomer such as (meth)acrylic acid or a (meth)acrylic acid ester as one component. Examples include resins obtained from acrylic monomers and copolymers of acrylic monomers with other monomers. Examples include acrylic-vinyl resins, which are copolymers of acrylic monomers and vinyl monomers. Another example of a vinyl monomer is styrene.

[0151] Examples of acrylic monomers that can be used include acrylamide and acrylonitrile. Commercially available products may be used for the resin emulsion using an acrylic resin as a raw material, such as FK-854 (trade name, manufactured by Chuo Rika Kogyo Co., Ltd.), Movinyl 952B, 718A, and 6760 (trade names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and Nipol LX852 and LX874 (trade names, manufactured by Nippon Zeon Co., Ltd.).

[0152] In this specification, the acrylic resin may be a styrene-acrylic resin, which will be described later. In addition, in this specification, the term "(meth)acrylic" means at least one of acrylic and methacrylic.

[0153] Styrene-acrylic resins are copolymers obtained from styrene monomer and (meth)acrylic monomer, and examples include styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, and styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer. As the styrene-acrylic resin, commercially available products may be used, such as JONCRYL 62J, 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, and 7610 (trade names, manufactured by BASF), Mowinyl 966A and 975N (trade names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and Vinyblan 2586 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0154] The polyolefin resin has an olefin such as ethylene, propylene, or butylene in its structural skeleton, and known polyolefin resins can be appropriately selected and used. As the olefin resin, commercially available products can be used, such as Arrowbase CB-1200 and CD-1200 (trade names, manufactured by Unitika Ltd.).

[0155] The resin particles may also be supplied in the form of an emulsion. Examples of commercially available resin emulsions include Microgel E-1002 and E-5002 (trade names of Nippon Paint Co., Ltd., styrene-acrylic resin emulsions), Boncoat 4001 (trade name of DIC Corporation, acrylic resin emulsion), Boncoat 5454 (trade name of DIC Corporation, styrene-acrylic resin emulsion), Polysol AM-710, AM-920, AM-2300, AP-4735, AT-860, and 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 K.K.), Polysol SAE1014 (trade name, styrene-acrylic resin emulsion, manufactured by Nippon Zeon Co., Ltd.), Saivinol SK-200 (trade name, acrylic resin emulsion, Saiden Chemical Co., Ltd.), AE-120A (JSR Corporation trade name, acrylic resin emulsion), AE373D (E-Tech Co., Ltd. trade name, carboxy-modified styrene-acrylic resin emulsion), Seikadyne 1900W (Dainichiseika Color & Chemicals Mfg. Co., Ltd. trade name, ethylene-vinyl acetate resin emulsion), Vinyblan 2682 (acrylic resin emulsion), Vinyblan 2886 (vinyl acetate-acrylic resin emulsion), Vinyblan 5202 (acetic acid acrylic resin emulsion) (Nissin Chemical Industry Co., Ltd. trade name), Elitel KA-5071S, KT-8803, K T-9204, KT-8701, KT-8904, KT-0507 (trade name of Unitika Ltd., polyester resin emulsion), Hi-Tec SN-2002 (trade name of Toho Chemical Co., Ltd., polyester resin emulsion), Takelac W-6020, W-635, W-6061, W-605, W-635, W-6021 (trade name of Mitsui Chemicals Polyurethanes, urethane resin emulsion), Superflex 870, 800, 150, 420, 420NS, 460, 470, 610, 700 (trade name of Daiichi Kogyo Seiyaku Co., Ltd., urethane resin emulsion),Permarin UA-150 (manufactured by Sanyo Chemical Industries, Ltd., urethane resin emulsion), Sancure 2710 (manufactured by The Lubrizol Corporation, urethane resin emulsion), NeoRez R-9660, R-9637, R-940 (manufactured by Kusumoto Chemicals Co., Ltd., urethane resin emulsion), Adeka Bontitor HUX-380, 290K (manufactured by ADEKA Corporation, urethane resin emulsion), Mowinyl 966A, Mowinyl 7320 (manufactured by The Nippon Synthetic Chemical Industry Co., Ltd.), Joncryl 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7 The binder may be selected from 630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, 7610 (all manufactured by BASF), NK Binder R-5HN (manufactured by Shin-Nakamura Chemical Co., Ltd.), Hydran WLS-210 (non-crosslinked polyurethane: manufactured by DIC Corporation), Joncryl 7610 (manufactured by BASF), and the like.

[0156] The glass transition temperature (Tg) of the resin particles is preferably -50°C or higher and 200°C or lower, more preferably 0°C or higher and 150°C or lower, and even more preferably 50°C or higher and 100°C or lower. 50°C or higher and 80°C or lower is particularly preferred. When the glass transition temperature (Tg) of the resin particles is within the above range, the durability and clogging resistance tend to be superior. The glass transition temperature is measured, for example, using a differential scanning calorimeter "DSC7000" manufactured by Hitachi High-Tech Science Corporation in accordance with JIS K7121 (Method for measuring transition temperature of plastics).

[0157] The volume average particle diameter of the resin particles is preferably 10 nm or more and 300 nm or less, more preferably 30 nm or more and 300 nm or less, even more preferably 30 nm or more and 250 nm or less, and particularly preferably 40 nm or more and 220 nm or less. The volume average particle diameter can be measured by the method described above.

[0158] The acid value of the resin contained in the resin particles is not particularly limited, but is preferably 1 to 300 KOHmg / g, more preferably 10 to 200 KOHmg / g, and even more preferably 20 to 100 KOHmg / g. When the acid value of the resin is within the above range, the resin particles tend to be anionic.

[0159] The content of resin particles in the colored ink is, relative to the total mass of the colored ink, from 0.1% by mass to 20% by mass, preferably from 1% by mass to 15% by mass, more preferably from 3% by mass to 7% by mass, and particularly preferably from 3% by mass to 5% by mass, in terms of solid content.

[0160] 1.3.1.(3) Water The colored ink contains water, which is the same as that described above for the reaction liquid, and therefore will not be described here.

[0161] 1.3.1.(4) Other ingredients The colored ink may contain components such as crosslinkers, organic solvents, surfactants, waxes, additives, pH adjusters, ureas, sugars, chelating agents, preservatives, mildew inhibitors, rust inhibitors, viscosity adjusters, antioxidants, antifungal agents, antioxidants, oxygen absorbers, dissolution aids, etc. These components are the same as those described for the reaction liquid above, so further description will be omitted.

[0162] Here, when the colored ink contains a crosslinking agent, the crosslinking agent is preferably anionic or nonionic, which can suppress aggregation of the crosslinking agent or resin in the colored ink and improve storage stability.

[0163] 1.3.1.(5) Physical Properties and Manufacturing of Colored Inks The colored ink is applied to the fabric by an inkjet method, and the viscosity of the colored ink at 20° C. is preferably 1.5 mPa·s or more and 15 mPa·s or less, more preferably 1.5 mPa·s or more and 7 mPa·s or less, and even more preferably 1.5 mPa·s or more and 5.5 mPa·s or less. When the colored ink is applied to the fabric by an inkjet method, it is easy to efficiently form a predetermined image on the fabric.

[0164] To ensure proper wetting and spreading of the colored ink onto fabric, the surface tension at 25° C. is 40 mN / m or less, preferably 38 mN / m or less, and more preferably 35 mN / m or less. The surface tension is preferably 20 mN / m or more, and more preferably 25 mN / m or more.

[0165] The surface tension can be measured by using an automatic surface tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) to check the surface tension when a platinum plate is wetted with the composition in an environment of 25°C.

[0166] The colored ink can be obtained by mixing the above-mentioned components in any order and, if necessary, removing impurities by filtration or the like. A suitable method for mixing the components is to add the materials sequentially to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stir and mix them. Filtration can be performed, if necessary, by centrifugal filtration, filter filtration, or the like.

[0167] 1.3.2.Method of applying colored ink to fabric The colored ink deposition step may be performed by any method according to the inkjet method in which the colored inks are deposited while scanning the inkjet head over the fabric. The inkjet method performs a main scan in which the inkjet head is moved in a direction perpendicular to the transport direction of the fabric to perform recording. The reaction liquid, the colored inks, and, if necessary, the clear ink may be deposited on the same scanned area of ​​the fabric by the same main scan.

[0168] The amount of colored ink applied in the colored ink application process is 0.12 mg / inch 2 As long as the range is equal to or greater than this, there are no particular limitations, and for example, 5.0 (mg / inch 2 ) or more is preferable. 2 ) or more is preferable, and 9.0 (mg / inch 2 ) or more is preferable.

[0169] The pigment coating amount is 0.12 mg / inch 2 Above, 0.15mg / inch 2 More preferably, it is 0.2 mg / inch or more. 2 More preferably, it is 0.3 mg / inch or more. 2 It is even more preferable that this is the case.

[0170] In addition, the upper limit of the amount of colored ink applied in the colored ink application process is 0.12 mg / inch 2 As long as the range is 50.0 (mg / inch or more), there are no particular limitations. 2 ) or less is preferable, and 40.0 (mg / inch 2 ) or less is more preferable, and 25.0 (mg / inch 2 ) The following is even more preferred.

[0171] The above-mentioned amount of color ink adhered is the amount in the recording region where the reaction liquid and the color ink are adhered in an overlapping manner in the inkjet printing method of this embodiment. It is also possible and preferred that the maximum amount of color ink adhered in this region be within the above-mentioned range.

[0172] 1.4. Crosslinker Distribution In the inkjet printing method of this embodiment, at least one of the reaction liquid and the colored ink contains a crosslinking agent. That is, only the reaction liquid, only the colored ink, or both the reaction liquid and the colored ink contain a crosslinking agent.

[0173] When either the reaction liquid or the colored ink contains a crosslinking agent, an image with good abrasion resistance can be formed. Furthermore, when both the reaction liquid and the colored ink contain a crosslinking agent, an image with even better abrasion resistance can be obtained. Furthermore, when both the reaction liquid and the colored ink contain a crosslinking agent, the content of each crosslinking agent can be reduced, thereby improving storage stability.

[0174] 1.5. Amount of crosslinkable functional group applied As described above, the crosslinking agent has crosslinkable functional groups. The amount of crosslinkable functional groups can be calculated from the number of crosslinkable functional groups per molecule of the crosslinking agent used and the molecular weight of the crosslinking agent used. The application amount of the crosslinkable functional groups can be calculated from the amount of crosslinkable functional groups in the crosslinking agent of each liquid, the concentration of the crosslinking agent, and the application amount of each liquid.

[0175] In the inkjet printing method of this embodiment, the amount of crosslinkable functional group applied is 0.05 mol / kg or more. The amount of crosslinkable functional group applied is preferably 0.08 mol / kg or more, more preferably 0.1 mol / kg or more, and even more preferably 0.12 mol / kg or more. The amount of crosslinkable functional group applied can be adjusted by the amount of reaction liquid and / or colored ink applied.

[0176] 1.6.Other processes 1.6.1. Transparent ink application process The inkjet printing method of this embodiment may include a transparent ink application step in which a transparent ink containing water and the resin that aggregates in the presence of the aggregating agent is ejected by an inkjet method to be applied to the fabric.

[0177] In the inkjet printing method of this embodiment, if the transparent ink application step is performed, an image with even better abrasion fastness can be obtained. In addition, by performing the transparent ink application step, the degree of freedom in the distribution of the crosslinking agent to the reaction liquid, colored inks, and transparent ink can be further increased.

[0178] 1.6.1.(1) Transparent ink The transparent ink contains water and a resin that aggregates with the aid of an aggregating agent. The transparent ink contains the same components as the colored inks described above, except that it does not contain any pigments.

[0179] (water) The transparent ink contains water, which is the same as that described above for the reaction liquid, and therefore will not be described here.

[0180] (resin) The clear ink contains a resin that aggregates with the aid of an aggregating agent. The resin contained in the clear ink is preferably resin particles. Details of the resin are the same as those described above for the colored inks, and therefore will not be described here.

[0181] (Other ingredients) The transparent ink may contain components such as crosslinkers, organic solvents, surfactants, waxes, additives, pH adjusters, ureas, sugars, chelating agents, preservatives, mildew inhibitors, rust inhibitors, viscosity adjusters, antioxidants, antifungal agents, antioxidants, oxygen absorbers, dissolution aids, etc. These components are the same as those described for the reaction liquid above, so further description will be omitted.

[0182] When the clear ink contains a crosslinking agent, the crosslinking agent is preferably anionic or nonionic, which can suppress aggregation of the crosslinking agent or resin in the clear ink and improve storage stability.

[0183] (Physical properties and manufacturing of transparent ink) The transparent ink has the same viscosity and surface tension as the colored inks described above, in that it is applied to the fabric by an inkjet method.

[0184] The clear ink can be obtained by mixing the above-mentioned components in any order and, if necessary, removing impurities by filtration or the like. A suitable method for mixing the components is to add the materials sequentially to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stir and mix them. As a filtration method, centrifugal filtration, filter filtration, etc. can be used as necessary.

[0185] (Method of applying transparent ink to fabric) The transparent ink application step may be performed by any method according to the inkjet method in which the transparent ink is applied while scanning the inkjet head over the fabric. The inkjet method performs a main scan in which the inkjet head is moved in a direction perpendicular to the transport direction of the fabric to perform recording. The reaction liquid, the colored inks, and the transparent ink may be applied to the same scanned area of ​​the fabric by the same main scan.

[0186] The amount of transparent ink applied in the transparent ink application step is not particularly limited, and may be, for example, 5.0 (mg / inch 2 ) or more is preferable. 2 ) or more is preferable, and 9.0 (mg / inch 2 ) or more is preferable.

[0187] The upper limit of the amount of transparent ink applied in the transparent ink application step is not particularly limited, and is 50.0 (mg / inch 2 ) or less is preferable, and 40.0 (mg / inch 2 ) or less is more preferable, and 25.0 (mg / inch 2 ) The following is even more preferred.

[0188] The amount of transparent ink applied is the amount in the recording region where the reaction liquid, colored inks, and transparent ink are applied in layers in the inkjet printing method of this embodiment. It is also possible and preferred that the maximum amount of transparent ink applied in this region be within the above range.

[0189] (Crosslinker Distribution) When the inkjet printing method according to this embodiment includes a clear ink application step, at least two of the reaction liquid, the colored ink, and the clear ink may contain a crosslinking agent, which improves the abrasion resistance of the resulting image.

[0190] If any one of the reaction liquid and the colored ink contains a crosslinking agent, an image with good abrasion fastness can be formed. On the other hand, if the inkjet printing method includes a clear ink application step, an image with good abrasion fastness can be formed even if at least two of the reaction liquid, colored ink, and clear ink contain a crosslinking agent. Furthermore, in this case, all of the reaction liquid, colored ink, and clear ink may contain a crosslinking agent. In this way, an image with even better abrasion fastness can be obtained. Furthermore, if all of the reaction liquid, colored ink, and clear ink contain a crosslinking agent, the content of each crosslinking agent can be reduced, thereby improving storage stability.

[0191] (Amount of crosslinkable functional group applied) In the inkjet printing method of this embodiment, even when a transparent ink application step is included, the coating amount of the crosslinkable functional group is 0.05 mol / kg or more. The coating amount of the crosslinkable functional group is preferably 0.08 mol / kg or more, more preferably 0.1 mol / kg or more, and even more preferably 0.12 mol / kg or more. The coating amount of the crosslinkable functional group can be adjusted by the coating amount of the reaction liquid and / or the colored ink and / or the transparent ink.

[0192] 1.6.2. Treatment liquid application process The inkjet printing method of this embodiment may include a treatment liquid application step in which a treatment liquid containing water and particles containing a forcibly emulsified organopolysiloxane or a specific substance selected from an aliphatic ester is ejected by an inkjet method and applied to a fabric.

[0193] 1.6.2.(1) Processing solution The treatment liquid contains particles containing forcibly emulsified organopolysiloxane, a specific substance selected from aliphatic esters, and water.

[0194] (Specified substance) The specific substance is selected from particles containing forcibly emulsified organopolysiloxane and aliphatic esters, and can function as a color former.

[0195] <Particles containing organopolysiloxane> The particles containing organopolysiloxane are not particularly limited as long as they contain organopolysiloxane, and may be, for example, organopolysiloxane particles themselves, or particles in which the organopolysiloxane is dispersed using an emulsifier or the like. The organopolysiloxane in such particles may be in the form of a solid or liquid. For example, when an oily organopolysiloxane is forcibly dispersed in water in the form of particles using an emulsifier, the dispersed particles correspond to particles containing organopolysiloxane.

[0196] Organopolysiloxanes are composed of siloxane bonds, "-Si(R 1 R 2 )-O-" skeleton, to which an organic group R 1 , R 2 Silicone is a general term for organosilicon compounds in which methyl, phenyl, vinyl, amino, and other groups are bonded. Depending on their chemical composition and molecular weight, organopolysiloxanes can be oily, rubbery, or resinous, and are sometimes called silicone oil, silicone rubber, and silicone resin, respectively.

[0197] The organopolysiloxane used in the treatment liquid is preferably an oily compound, since if the organopolysiloxane is an oily compound, it can be easily dispersed stably in particulate form in an aqueous matrix by forced emulsification.

[0198] The molecular structure of the organopolysiloxane is not particularly limited, and examples include linear, branched, cyclic, lattice, cage, etc. When the molecular structure of the organopolysiloxane is acyclic, one or more groups selected from optionally substituted hydrocarbon groups, alkoxy groups, hydroxyl groups, hydrogen atoms, and halogens are usually bonded to the terminal Si atoms of the molecule.

[0199] The organopolysiloxane is not particularly limited, but examples thereof include dimethyl silicone, alkyl-modified silicone, amino-modified silicone, epoxy-modified silicone, cyclic silicone, and methylphenyl silicone, which can be used alone or in combination of two or more.

[0200] Alternatively, commercially available organopolysiloxanes may be used as silicone oils, examples of which include dimethylsilicone oil, methylphenylsilicone oil, methylhydrogensilicone oil, polyether-modified silicone oil, aralkyl-modified silicone oil, fluoroalkyl-modified silicone oil, long-chain alkyl-modified silicone oil, higher fatty acid ester-modified silicone oil, higher fatty acid amide-modified silicone oil, polyether-long-chain alkyl-aralkyl-modified silicone oil, long-chain alkyl-aralkyl-modified silicone oil, phenyl-modified silicone oil, and polyether-methoxy-modified silicone oil.

[0201] Of the organopolysiloxanes listed above, nonionic silicones are more preferred. Of the organopolysiloxanes listed above, unmodified silicones are more preferred. Such organopolysiloxanes are chemically more stable and are less likely to cause yellowing of the formed image.

[0202] Furthermore, the organopolysiloxane is more preferably one or more selected from dimethyl silicone, methyl phenyl silicone, and methyl hydrogen silicone.

[0203] Examples of commercially available silicone oils include dimethyl silicone (KF-96 series, manufactured by Shin-Etsu Chemical Co., Ltd.), methyl hydrogen polysiloxane (KF-99 series, KF-9901, etc., manufactured by Shin-Etsu Chemical Co., Ltd.), methyl phenyl silicone (KF-50 series, etc., manufactured by Shin-Etsu Chemical Co., Ltd.), amino-modified silicone (KF-868, etc., manufactured by Shin-Etsu Silicones), and branched silicone silicone treatment agents (KF-9908, KF-9909, etc., manufactured by Shin-Etsu Chemical Co., Ltd.).

[0204] The viscosity of the silicone at 25°C is not particularly limited, but is preferably 1000 mPa·s or less, and also preferably 50 mPa·s or more, more preferably 500 mPa·s or more and 900 mPa·s or less, and even more preferably 600 mPa·s or more and 700 mPa·s or less. Furthermore, the viscosity of the base oil in which the silicone is emulsified and dispersed is not particularly limited, but the upper limit is preferably 1000000 mm 2 / s or less, more preferably 100,000 mm 2 / s or less, the lower limit is preferably 10 mm 2 / s or more, preferably 100 mm 2 / s or more. Base oil viscosity indicates the viscosity of the base oil and is a value that measures the internal resistance of the base oil. The higher the base oil viscosity value, the higher the viscosity, and the lower the value, the lower the viscosity of the base oil.

[0205] The organopolysiloxane may be blended in particulate form by emulsifying it with various surfactants as emulsifiers. This is sometimes referred to as forced emulsification in this specification. Examples of emulsifiers that can be used in this case include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and phospholipids.

[0206] Examples of nonionic surfactants include glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, sorbitan fatty acid esters, and sorbitol fatty acid esters, as well as alkylene glycol adducts thereof, polyalkylene glycol fatty acid esters, sucrose fatty acid esters, polysorbate 20, polysorbate 60, polysorbate 80, polyoxyalkylene alkyl ethers, and polyoxyethylene alkylphenyl ethers.

[0207] Furthermore, as the nonionic surfactant, for example, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytosterol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, polyoxyethylene beeswax derivative, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene alkylphenyl formaldehyde condensate, polyoxyethylene alkyl ether phosphate (salt), and the like are also suitable for use.

[0208] Examples of anionic surfactants include alkyl sulfate ester salts, polyoxyethylene alkyl sulfate ester salts, alkylbenzene sulfonates, and α-olefin sulfonates. Examples of cationic surfactants include alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, and benzalkonium chloride. Examples of amphoteric surfactants include alkyldimethylaminoacetic acid betaine and alkylamidodimethylaminoacetic acid betaine. Furthermore, naturally occurring surfactants may be used, such as lecithin, lanolin, cholesterol, and saponin.

[0209] The amount of emulsifier used when emulsifying the organopolysiloxane is preferably less than 20% by mass, more preferably 15% by mass or less, and particularly preferably 10% by mass or less, of the total amount of the emulsion composition.

[0210] The average particle size of the emulsified particulate organopolysiloxane particles is preferably 2 μm or less, more preferably 1 μm or less, and even more preferably in the range of 0.05 to 0.5 μm.

[0211] <Fatty acid ester> Examples of fatty acid esters include polyoxyethylene monocaprate, polyoxyethylene monocaprylate, polyoxyethylene monolaurate, polyoxyethylene monomyristate, polyoxyethylene monopalmitate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyoxyethylene monoisostearate, polyoxyethylene monobehenate, polyoxyethylene dicaprate, polyoxyethylene dicaprylate, polyoxyethylene dilaurate, polyoxyethylene dimyristate, polyoxyethylene dipalmitate, polyoxyethylene distearate, polyoxyethylene dioleate, polyoxyethylene diisostearate, and polyoxyethylene dibehenate.

[0212] Furthermore, it is more preferable that the specific substance is at least one selected from particles containing forcibly emulsified organopolysiloxane, which allows the treatment liquid to impart a water-repellent effect to the fibers of the fabric, thereby further improving the abrasion resistance of the image on the recorded material.

[0213] Furthermore, when particles containing organopolysiloxane are selected as the specific substance, the organopolysiloxane is preferably a nonionic silicone, which can further reduce yellowing of the printed matter.

[0214] Furthermore, when particles containing organopolysiloxane are selected as the specific substance, it is also preferable that the organopolysiloxane is an amino-modified silicone, which can further suppress bleeding of the treatment liquid.

[0215] The content of the specific substance in the treatment liquid is 60% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 70% by mass or more, based on the total amount of non-volatile components in the treatment liquid.

[0216] (water) The treatment liquid contains water, which is the same as that described above for the reaction liquid, and therefore further explanation will be omitted.

[0217] (Other ingredients) The treatment liquid may contain components such as organic solvents, surfactants, waxes, additives, pH adjusters, ureas, sugars, chelating agents, preservatives, mildew inhibitors, rust inhibitors, viscosity adjusters, antioxidants, antifungal agents, antioxidants, oxygen absorbers, dissolution aids, etc. These components are the same as those described for the reaction liquid above, so further description will be omitted.

[0218] (Properties and production of processing liquid) The treatment liquid is applied to the fabric by an inkjet method, and therefore has the same viscosity and surface tension as the above-mentioned transparent ink.

[0219] The treatment liquid can be obtained by mixing the above-mentioned components in any order and removing impurities by filtration, etc., as needed. A suitable method for mixing the components is to add the materials sequentially to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stir and mix them. As a filtration method, centrifugal filtration, filter filtration, etc. can be used as needed.

[0220] (Method of applying a treatment liquid to fabric) The treatment liquid application step may be performed by any method according to an inkjet method in which the treatment liquid is applied to the fabric while the inkjet head is scanned over the fabric. The inkjet method performs a main scan in which the inkjet head is moved in a direction perpendicular to the fabric transport direction to perform recording. The reaction liquid, colored ink, clear ink, and treatment liquid may be applied to the same scanned area of ​​the fabric by the same main scan.

[0221] The amount of the treatment liquid applied in the treatment liquid application step is not particularly limited, and may be, for example, 5.0 (mg / inch 2 ) or more is preferable. 2 ) or more is preferable, and 9.0 (mg / inch 2 ) or more is preferable.

[0222] The upper limit of the amount of treatment liquid applied in the treatment liquid application step is not particularly limited, and is 50.0 (mg / inch 2 ) or less is preferable, and 40.0 (mg / inch 2 ) or less is more preferable, and 25.0 (mg / inch 2 ) The following is even more preferred.

[0223] 1.6.3.Drying process The inkjet printing method according to this embodiment may include a drying step between, before, or after each of the above-described steps. The drying step can be performed by a drying means using a drying mechanism. Examples of drying means using a drying mechanism include a means for blowing room temperature air or hot air onto the fabric (air blowing type), a means for irradiating the fabric with radiation (infrared rays, etc.) that generates heat (radiation type), a member that contacts the fabric and transfers heat to the fabric (conduction type), and a combination of two or more of these means. When a drying step is included, it is preferably performed by a drying mechanism that heats the fabric. When a drying mechanism that heats the fabric is used as the drying mechanism, it is particularly referred to as a heating step.

[0224] The surface temperature of the fabric when each composition is applied is preferably 45°C or lower, more preferably 10°C to 45°C. It is also preferably 15°C to 40°C, more preferably 20°C to 30°C. This temperature is the surface temperature of the portion of the recording surface of the fabric that receives the liquid during the application process, and is the highest temperature in the recording area during the application process. A surface temperature within the above range is more preferable in terms of image quality, abrasion resistance, and reduced clogging.

[0225] The method for heating the fabric is not particularly limited, but examples thereof include heat pressing, atmospheric pressure steaming, high-pressure steaming, and Thermofix. The heat source for heating is not particularly limited, but for example, an infrared lamp can be used. The heating temperature is preferably a temperature at which the resin particles in the ink are fused and the medium, such as water, volatilizes. For example, it is preferably 100°C or higher and 200°C or lower, more preferably 170°C or lower, and even more preferably 160°C or lower. Here, the heating temperature in the heating step refers to the surface temperature of an image or the like formed on the fabric. The heating time is not particularly limited, but is, for example, 30 seconds to 20 minutes.

[0226] It is also preferable to not have a drying step, which may allow images with good color development to be obtained in a shorter time.

[0227] 1.7. Crosslinker content In the inkjet printing method of this embodiment, any of the reaction liquid, colored ink, and clear ink may contain a crosslinking agent.

[0228] When the inkjet printing method of this embodiment does not include a clear ink application step, the content of the crosslinking agent in both the reaction liquid and the colored inks is preferably 10% by mass or less, more preferably 9% by mass or less, and even more preferably 8% by mass or less. In this way, the crosslinking agent is not contained in too much amount in the reaction liquid and the colored inks, and therefore the storage stability of each is less likely to decrease.

[0229] When the inkjet printing method of this embodiment includes a clear ink application step, the content of the crosslinking agent in each of the reaction liquid, the colored inks, and the clear ink is preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less. In this way, the crosslinking agent is not contained in too much of the reaction liquid, the colored inks, and the clear ink, so that the storage stability of each is less likely to decrease.

[0230] Furthermore, in the inkjet printing method of this embodiment, the content of the crosslinking agent, in total, of the reaction liquid, colored ink, and clear ink, relative to the total amount of the three liquids, is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 8% by mass or more. When the crosslinking agent is contained in only one liquid, it is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 8% by mass or more, relative to the total amount of the liquids used for recording. Even when the crosslinking agent is contained in only two liquids, it is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 8% by mass or more, relative to the total amount of the liquids used for recording. This results in better abrasion resistance and better color development of the resulting image.

[0231] 1.8. Time interval between processes In the inkjet printing method of this embodiment, the time interval between the reaction liquid application step and the colored ink application step is preferably 5 seconds or less, more preferably 3 seconds or less, and even more preferably 1 second or less.

[0232] The time interval can be adjusted by the structure and operation of the recording device. For example, if the recording device is a serial type, it can be adjusted by changing the main scanning speed, interval, etc. Furthermore, if the recording device is a line type, it can be adjusted by changing the fabric transport speed, the interval between recording heads, etc.

[0233] If the time interval between the reaction liquid application step and the colored ink application step is within the above range, the time interval between the reaction liquid application step and the colored ink application step is short, and therefore the colored ink is likely to land before the reaction liquid permeates into the fabric, thereby obtaining an image of better quality.

[0234] 1.9.Amount of resin applied In the inkjet printing method of this embodiment, both the colored ink and the transparent ink may contain a resin.

[0235] When the inkjet printing method of this embodiment does not include the transparent ink application step, the coating amount of the resin that is aggregated by the aggregating agent contained in the colored ink is 0.4 mg / inch 2 It is preferable that the concentration is 0.5 mg / inch or more. 2 More preferably, it is 0.6 mg / inch or more. 2 It is more preferable that the above ratio is satisfied. In this way, the rub resistance of the obtained image is improved.

[0236] When the inkjet printing method of this embodiment includes a transparent ink application step, the total application amount of the resin that aggregates due to the aggregation agent contained in the colored ink and the resin that aggregates due to the aggregation agent contained in the transparent ink is 0.4 mg / inch. 2 It is preferable that the concentration is 0.5 mg / inch or more. 2 More preferably, it is 0.6 mg / inch or more. 2 It is more preferable that the above ratio is satisfied. In this way, the rub resistance of the obtained image is improved.

[0237] 1.10. Effects, etc. In the inkjet printing method of this embodiment, at least one of the reaction liquid and the colored ink contains a crosslinking agent, and the coating amount of the pigment is 0.12 mg / inch. 2 The above procedure is carried out so that the amount of crosslinkable functional group applied is 0.05 mol / kg or more.

[0238] The resin in the colored ink aggregates due to the aggregating agent in the reaction liquid, contributing to improved fastness. However, sufficient fastness may not be achieved, particularly when each liquid is applied continuously without a drying process. Furthermore, in image areas where the amount of pigment applied is large, dark colors can be expressed, but the abrasion fastness tends to be insufficient. However, according to the inkjet printing method of this embodiment, by incorporating a crosslinking agent in at least one of the reaction liquid and the colored ink and setting the amount of crosslinkable functional group applied to 0.05 mol / kg or more, the abrasion fastness of the resulting image can be improved.

[0239] 2. Ink set The ink set according to this embodiment includes a reaction liquid containing an aggregating agent and water, a colored ink containing a pigment, water, and a resin that aggregates in the presence of the aggregating agent, and a clear ink containing water and a resin that aggregates in the presence of the aggregating agent.

[0240] At least two of the reaction liquid, the colored ink, and the transparent ink contain a crosslinking agent, and the coating amount of the pigment is 0.12 mg / inch 2 The composition is used by being ejected by an ink jet method so that the amount of crosslinkable functional groups applied is 0.05 mol / kg or more and attached to the fabric.

[0241] According to the ink set of this embodiment, a crosslinking agent is contained in at least one of the reaction liquid and the colored ink, and the coating amount of the crosslinkable functional group is set to 0.05 mol / kg or more, thereby making it possible to obtain images with good abrasion resistance.

[0242] 3. Recording device The inkjet printing method according to this embodiment includes a step of ejecting and depositing the above-described reaction liquid and colored inks by an inkjet method. The inkjet printing method according to this embodiment may also include a step of ejecting and depositing the above-described clear ink and treatment liquid by an inkjet method, as necessary.

[0243] An example of an inkjet textile printing apparatus (recording apparatus) equipped with an inkjet head that can be applied to the inkjet textile printing method according to this embodiment will be described with reference to FIG.

[0244] In Fig. 1, the scale of each layer and each component is different from the actual scale so that each layer and each component can be recognized. For ease of explanation, Fig. 1 illustrates three mutually perpendicular axes: the X-axis, the Y-axis, and the Z-axis. The tip of the arrow indicating the axial direction is designated as the "+ side," and the base is designated as the "- side." The direction parallel to the X-axis is designated as the "X-axis direction," the direction parallel to the Y-axis is designated as the "Y-axis direction," and the direction parallel to the Z-axis is designated as the "Z-axis direction."

[0245] 3.1.Overall schematic structure 1 is a schematic diagram showing the overall configuration of a recording device 100. First, the overall configuration of the recording device 100 will be described with reference to FIG.

[0246] 1, the recording device 100 includes a medium transport unit 20, a medium contact unit 60, a belt support unit 91, a printing unit 40, a heating unit 27, a cleaning unit 50, and the like. In the recording device 100, at least one of the medium contact unit 60 and the belt support unit 91 corresponds to a heating unit that heats the endless belt 23. The recording device 100 also includes a control unit 1 that controls each of these units. Each unit of the recording device 100 is attached to a frame unit 90.

[0247] When a heating unit for heating the endless belt is provided, it need only be located upstream of the printing unit 40 in the transport direction, and may be located in a location different from the medium contact unit 60 and the belt support unit 91. For example, the heating unit may be located upstream of the medium contact unit 60 in the transport direction. With this configuration, the heating unit can also dry the endless belt 23 that becomes wet during cleaning. The heating unit may also heat the endless belt without contacting it.

[0248] The medium transport unit 20 transports the fabric 95 in the transport direction. The medium transport unit 20 includes a medium supply unit 10, transport rollers 21 and 22, an endless belt 23, a belt rotation roller 24, a belt drive roller 25 as a drive roller, transport rollers 26 and 28, and a medium recovery unit 30.

[0249] 3.2. Media transport section First, the transport path of the fabric 95 from the medium supply unit 10 to the medium collection unit 30 will be described. In Fig. 1, the direction along the direction of gravity is the Z-axis direction, the direction in which the fabric 95 is transported in the printing unit 40 is the +X-axis direction, and the width direction of the fabric 95 that intersects with both the Z-axis direction and the X-axis direction is the Y-axis direction. In addition, the positional relationship along the transport direction of the fabric 95 or the movement direction of the endless belt 23 is also referred to as the "upstream side" and the "downstream side."

[0250] The medium supply unit 10 supplies the fabric 95 on which an image is to be formed to the printing unit 40. The medium supply unit 10 has a supply shaft 11 and a bearing 12. The supply shaft 11 is formed in a cylindrical or columnar shape and is rotatable in the circumferential direction. A strip-shaped fabric 95 is wound around the supply shaft 11 in a roll. The supply shaft 11 is detachably attached to the bearing 12. As a result, the fabric 95, which has been wound around the supply shaft 11 in advance, can be attached to the bearing 12 together with the supply shaft 11.

[0251] Bearings 12 rotatably support both axial ends of supply shaft 11. Medium supply unit 10 has a rotation drive unit (not shown) that rotates supply shaft 11. The rotation drive unit rotates supply shaft 11 in the direction in which fabric 95 is fed out. The operation of the rotation drive unit is controlled by control unit 1. Conveyor rollers 21 and 22 relay fabric 95 from medium supply unit 10 to endless belt 23.

[0252] The endless belt 23 is held between at least two rollers that rotate the endless belt 23, and the rotational movement of the endless belt 23 supports and transports the fabric 95 in the transport direction (+X-axis direction). More specifically, the endless belt 23 is a seamless belt formed by seamlessly connecting both ends of a strip-shaped belt, and is hung between two rollers, a belt rotation roller 24 and a belt drive roller 25.

[0253] The endless belt 23 is held under a predetermined tension so that the portion between the belt rotation roller 24 and the belt drive roller 25 is horizontal. An adhesive 29 that adheres the fabric 95 is applied to the surface (support surface) 23a of the endless belt 23. That is, the endless belt 23 has an adhesive layer made of the adhesive 29. The fabric 95 is attached to the endless belt 23 via the adhesive 29. The endless belt 23 is supplied from the transport roller 22 and supports (holds) the fabric 95 that is in contact with the adhesive 29 at a medium contacting section 60 described below.

[0254] It is preferable that adhesive 29 has adhesiveness that increases when heated. By using adhesive 29 whose adhesiveness increases when heated, fabric 95 can be well adhered to the adhesive layer. An example of such adhesive 29 is a hot-melt adhesive containing thermoplastic elastomer SIS (styrene-isoprene-styrene) as a main component.

[0255] The belt rotation roller 24 and the belt drive roller 25 support the inner circumferential surface 23b of the endless belt 23. A contact portion 69, a belt support portion 91, and a platen 46 that support the endless belt 23 are provided between the belt rotation roller 24 and the belt drive roller 25. The contact portion 69 is provided in an area facing a pressing portion 61 (described later) across the endless belt 23, the platen 46 is provided in an area facing a printing portion 40 across the endless belt 23, and the belt support portion 91 is provided between the contact portion 69 and the platen 46. The contact portion 69, the belt support portion 91, and the platen 46 support the endless belt 23, thereby making it possible to suppress vibration of the endless belt 23 that occurs when the endless belt 23 is moved.

[0256] The belt drive roller 25 is a drive unit that rotates the endless belt 23 to transport the fabric 95 in the transport direction, and has a motor (not shown) that rotates the belt drive roller 25. The belt drive roller 25 is provided downstream of the printing unit 40 in the transport direction of the fabric 95, and the belt rotation roller 24 is provided upstream of the printing unit 40. When the belt drive roller 25 is driven to rotate, the endless belt 23 rotates in accordance with the rotation of the belt drive roller 25, and the rotation of the endless belt 23 rotates the belt rotation roller 24. The rotation of the endless belt 23 transports the fabric 95 supported by the endless belt 23 in the transport direction (positive X-axis direction), and an image is formed on the fabric 95 in the printing unit 40, which will be described later.

[0257] 1, fabric 95 is supported on the side (+Z axis side) where surface 23a of endless belt 23 faces printing unit 40, and fabric 95 is transported together with endless belt 23 from the belt rotation roller 24 side to the belt drive roller 25 side. Furthermore, on the side (-Z axis side) where surface 23a of endless belt 23 faces cleaning unit 50, only endless belt 23 moves from the belt drive roller 25 side to the belt rotation roller 24 side.

[0258] The transport roller 26 peels the fabric 95 on which the image has been formed from the adhesive 29 of the endless belt 23. The transport rollers 26 and 28 relay the fabric 95 from the endless belt 23 to the medium recovery unit 30.

[0259] The medium collection unit 30 collects the fabric 95 transported by the medium transport unit 20. The medium collection unit 30 has a winding shaft 31 and a bearing 32. The winding shaft 31 is formed in a cylindrical or columnar shape and is rotatable in the circumferential direction. A strip-shaped fabric 95 is wound up in a roll around the winding shaft 31. The winding shaft 31 is detachably attached to the bearing 32. This allows the fabric 95 wound up around the winding shaft 31 to be removed together with the winding shaft 31.

[0260] The bearings 32 rotatably support both axial ends of the winding shaft 31. The medium collection unit 30 has a rotation drive unit (not shown) that rotates the winding shaft 31. The rotation drive unit rotates the winding shaft 31 in the direction in which the fabric 95 is wound. The operation of the rotation drive unit is controlled by the control unit 1.

[0261] Next, the heating section, printing section 40, heating unit 27, and cleaning unit 50, which are provided along the medium transport section 20, will be described.

[0262] 3.3. Heating section It is preferable that a heater for heating the endless belt 23 is provided in at least one of the contact portion 69 and the belt support portion 91. The heater constitutes a heating portion. When a heater is provided in the contact portion 69, the pressing portion 61 can apply pressing force and heat to the endless belt 23, which is preferable in that it can improve the adhesion of the fabric 95 to the endless belt 23. Therefore, when a heater is provided in either the contact portion 69 or the belt support portion 91, it is more preferable to provide the heater in the contact portion 69.

[0263] The heating section heats the adhesive layer to soften it and make it more adhesive, thereby improving the adhesion between the adhesive layer and the fabric 95. This prevents the fabric 95 from moving on the endless belt 23, and allows for good conveyance accuracy.

[0264] When a heater is provided in at least one of the contact portion 69 and the belt support portion 91 and the endless belt 23 is heated, the temperature of the surface 23a of the endless belt 23 is preferably 80°C or less, more preferably 70°C or less, and even more preferably 60°C or less. If the temperature of the surface 23a of the endless belt 23 is within the above range, the reactivity of the resin particles contained in the ink may be suppressed, making it easier to clean the belt. The lower limit of the temperature of the surface 23a of the endless belt 23 may be any temperature that allows the adhesive layer to exhibit adhesiveness, and is preferably 30°C or more, more preferably 35°C or more, and even more preferably 40°C or more. The temperature of the surface 23a of the endless belt 23 can be measured using, for example, a radiation thermometer or a contact thermometer, and measurement using a radiation thermometer is more preferable.

[0265] When a heater is provided on at least one of the contact portion 69 and the belt support portion 91, a temperature detection portion (not shown) may be provided to detect the surface temperature of the endless belt 23. The temperature detection portion may be, for example, a thermocouple. This allows the control portion 1 to control the heater based on the temperature detected by the temperature detection portion, thereby maintaining the endless belt 23 at a predetermined temperature. Note that the temperature detection portion may be a non-contact thermometer that uses infrared rays.

[0266] 3.4.Printing Department The printing unit 40 is disposed above (on the +Z axis side) the position of the endless belt 23, and performs printing on the fabric 95 placed on the surface 23a of the endless belt 23. The printing unit 40 has an inkjet head 42, a carriage 43 on which the inkjet head 42 is mounted, a carriage moving unit 45 that moves the carriage 43 in the width direction (Y axis direction) of the fabric 95 that intersects with the conveyance direction, and the like.

[0267] The inkjet head 42 is a means for spraying and adhering a liquid composition supplied from a liquid cartridge (not shown) from a plurality of nozzles onto the fabric 95 under the control of the control unit 1. The inkjet head 42 has a plurality of nozzles that eject the liquid composition onto the fabric 95 to which the liquid composition is to be applied. These plurality of nozzles are arranged in a row to form a nozzle row, and the nozzle rows are individually arranged corresponding to the liquid compositions. The liquid composition is supplied from each liquid cartridge to the inkjet head 42 and ejected as droplets from the nozzles by an actuator (not shown) within the inkjet head 42. The ejected droplets of the liquid composition land on the fabric 95, forming an image, text, a pattern, a color, etc. in the printing area of ​​the fabric 95.

[0268] The liquid composition referred to here can be the above-mentioned reaction liquid, colored ink, transparent ink, treatment liquid, etc. The types and numbers of these liquid compositions can be set appropriately.

[0269] In the inkjet head 42, a piezoelectric element is used as an actuator, which is a driving means, but the invention is not limited to this. For example, an electromechanical transducer element that displaces a vibration plate as an actuator by electrostatic adsorption, or an electrothermal transducer element that ejects a liquid composition or the like as droplets by bubbles generated by heating may also be used.

[0270] The carriage moving unit 45 is provided above (on the +Z-axis side of) the endless belt 23. The carriage moving unit 45 has a pair of guide rails 45a, 45b extending along the Y-axis direction. The inkjet head 42 is supported by the guide rails 45a, 45b in a state in which it can move back and forth together with the carriage 43 along the Y-axis direction.

[0271] The carriage moving unit 45 includes a moving mechanism and a power source (not shown). The moving mechanism may be, for example, a mechanism that combines a ball screw and a ball nut, or a linear guide mechanism. Furthermore, the carriage moving unit 45 includes a motor (not shown) as a power source for moving the carriage 43 along the guide rails 45a and 45b. Various motors, such as a stepping motor, a servo motor, or a linear motor, may be used as the motor. When the motor is driven under the control of the control unit 1, the inkjet head 42 moves along the Y-axis direction together with the carriage 43.

[0272] 3.5.Heating unit A heating unit 27 may be provided between the transport roller 26 and the transport roller 28. The heating unit 27 heats the ink composition, softening liquid composition, or coating liquid composition ejected onto the fabric 95. This tends to allow the reaction of the resin particles contained in the ink composition to proceed sufficiently. By allowing the resin particles to react sufficiently, an image with good abrasion resistance may be formed. The heating unit 27 may also be used for the purpose of drying the fabric 95. The heating unit 27 includes, for example, an IR heater, and by driving the IR heater, the ink composition or coating liquid composition ejected onto the fabric 95 can be reacted in a short period of time. This allows the strip-shaped fabric 95 on which an image or the like is formed to be wound around the winding shaft 31.

[0273] 3.6.Cleaning unit The cleaning unit 50 is disposed between the belt rotation roller 24 and the belt drive roller 25 in the X-axis direction. The cleaning unit 50 has a cleaning section 51, a pressing section 52, and a moving section 53. The moving section 53 moves the cleaning unit 50 integrally along the floor surface 99 and fixes it in a predetermined position.

[0274] The pressing unit 52 is, for example, an elevating device made up of an air cylinder 56 and a ball bushing 57, and brings the cleaning unit 51 provided on the upper part thereof into contact with the surface 23a of the endless belt 23. The cleaning unit 51 is hung between the belt rotation roller 24 and the belt drive roller 25 with a predetermined tension applied, and cleans the surface (support surface) 23a of the endless belt 23 moving from the belt drive roller 25 toward the belt rotation roller 24 from below (in the −Z axis direction).

[0275] The cleaning unit 51 has a cleaning tank 54, a cleaning roller 58, and a blade 55. The cleaning tank 54 is a tank that stores a cleaning liquid used to clean ink and foreign matter adhering to the surface 23a of the endless belt 23, and the cleaning roller 58 and the blade 55 are provided inside the cleaning tank 54. As the cleaning liquid, for example, water or a water-soluble solvent (such as an alcohol aqueous solution) can be used, and a surfactant or an antifoaming agent may be added as needed.

[0276] When the cleaning roller 58 rotates, the cleaning liquid is supplied to the surface 23a of the endless belt 23, and the cleaning roller 58 slides against the endless belt 23. As a result, the ink composition and fibers of the fabric 95 adhering to the endless belt 23 are removed by the cleaning roller 58.

[0277] The blade 55 can be made of a flexible material such as silicone rubber. The blade 55 is provided downstream of the cleaning roller 58 in the conveyance direction of the endless belt 23. The cleaning liquid remaining on the surface 23a of the endless belt 23 is removed by sliding between the endless belt 23 and the blade 55.

[0278] According to such a recording apparatus 100, the inkjet printing method of this embodiment can be easily carried out.

[0279] 4. Examples and Comparative Examples The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Hereinafter, "parts" and "%" are based on mass unless otherwise specified. The evaluations were carried out in an environment of a temperature of 25°C and a relative humidity of 40.0%, unless otherwise specified.

[0280] 4.1. Preparation of each liquid The reaction liquid, colored ink, and clear ink for each example were prepared as follows. The materials were mixed in the compositions shown in Tables 1 to 3 and thoroughly stirred to obtain each liquid. The values ​​shown are solid content concentrations in mass %, and the total is 100.0 mass %.

[0281] The abbreviations and product names shown in Tables 1 to 3 are explained below. Magnesium sulfate: polyvalent metal salt Olfine E1010: Olfine E1010: Nissin Chemical Industry Co., Ltd. Acetylene glycol surfactant EDTA-2Na: Ethylenediaminetetraacetic acid disodium salt Proxel XL2: Lonza Japan Co., Ltd. Antiseptic and antifungal agent Meikanate CX: Meisei Chemical Industry Co., Ltd., blocked isocyanate (HDI-based cationic) Trixene AQUA BI220: GSI Creos Corporation, blocked isocyanate (HDI-based nonionic) Meikanate TP-10: Blocked isocyanate (TDI-based anionic) manufactured by Meisei Chemical Industry Co., Ltd. EPOCROS K2010E: Nippon Shokubai Co., Ltd., oxazoline group-containing polymer BONJET BLACK CW-1: Black color material Superflex 420NS: urethane resin emulsion manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0282] Furthermore, a processing liquid (color former) was used in Example 8. The composition of the processing liquid was as follows: The following components were mixed and thoroughly stirred to obtain a processing liquid. Glycerin 20% by mass Propylene glycol 1% by mass Dimethyl silicone oil 7% by mass (Dimethyl silicone oil: Shin-Etsu Silicone Co., Ltd., KF-96H-10,000cs) ·Olfine E1010 1% by mass Water Residual

[0283] Tables 1 to 3 show the liquid injection ratio and the amount of color material (mg / inch) in the pattern for each example. 2 ), the difference in time (seconds) between the impact of the reaction liquid and the colored ink, the total amount of crosslinking agent on the fabric (mass%), and the amount of functional groups on the fabric (mol / kg) were also recorded.

[0284] In Example 8, the ratio of each liquid injected (reaction liquid: colored ink: transparent ink: treatment liquid) was 1:1:1:1.

[0285] 4.2.Evaluation Method 4.2.1. Creating printed items A modified SC-F2150 (Seiko Epson Corporation) was used for printing. 50% cotton, 50% polyester broadcloth and 100% polyester satin were used as recording media. A head unit (600 dpi nozzle spacing across the recording medium, 600 nozzles) was used. The recording conditions (discharge ratio of ink, etc.) were as shown in the table. A printed material was produced in which a solid pattern image was formed (ink printed) on an A4-sized piece of fabric, the recording medium. Here, "solid pattern image" refers to an image in which dots are printed in all pixels, which is the minimum recording unit area defined by the recording resolution. The (100% duty) printed material was heat-treated in an oven at 160°C for 3 minutes and dried.

[0286] 4.2.2. Friction resistance The printed fabric was tested for rubbing fastness using a test method in accordance with ISO105-X12, and the wet rubbing fastness was evaluated according to the following criteria, with the results shown in Tables 1 to 3. Evaluation results of C or higher indicate good color development. A: Level 3-4 or higher B: 3rd grade C:2-3 grade D: Level 2 or below

[0287] 4.2.3.Evaluation of color development The black OD value of the printed fabric was measured using a fluorescence spectrodensitometer (FD-7, manufactured by Konica Minolta) to evaluate color development, and the results are shown in Tables 1 to 3. Evaluation results of C or higher indicate good color development. A:OD value is 1.45 or more B: OD value is 1.40 or more and less than 1.45 C:OD value is 1.35 or more and less than 1.40 D:OD value is less than 1.35

[0288] 4.2.4. Evaluation of texture The shear hardness (gf / cm⋅degree) of the printed fabric was tested using a tensile shear tester (KES-FB1-A, manufactured by Kato Tech Co., Ltd.) and evaluated according to the following criteria, with the results shown in Tables 1 to 3. Evaluation results of C or higher indicate a good texture. S: Shear hardness less than 7 B: Shear hardness is 7 or more and less than 10 C: Shear hardness is 10 or more and less than 15 D: Shear hardness is 15 or more

[0289] 4.2.5. Evaluation of storage stability 30 ml of each solution was placed in a 30 ml sample bottle, and the viscosity was measured using a rheometer after leaving it at 60°C for one week. The rate of change was measured. The results were evaluated according to the following criteria and are shown in the table. A: Viscosity change is less than 3% B: Viscosity change is 3% or more but less than 5% C: Viscosity change is 5% or more but less than 10% D: Viscosity change is 10% or more

[0290] 4.3.Evaluation Results Each table shows that the method includes a reaction liquid application step in which a reaction liquid containing a flocculant and water is ejected by an inkjet method and applied to a fabric, and a colored ink application step in which a colored ink containing a pigment, water, and a resin that is flocculated by the flocculant is ejected by an inkjet method and applied to a fabric, and at least one of the reaction liquid and the colored ink contains a crosslinking agent, and the coating amount of the pigment is 0.12 mg / inch. 2 As described above, it was found that in the ink-jet printing of each example in which the coating amount of the crosslinkable functional group was 0.05 mol / kg or more, images with good rub fastness were obtained.

[0291] The present invention includes configurations that are substantially the same as the configurations described in the embodiments, for example, configurations with the same functions, methods, and results, or configurations with the same purpose and effects. The present invention also includes configurations that replace non-essential parts of the configurations described in the embodiments. The present invention also includes configurations that achieve the same effects or purposes as the configurations described in the embodiments. The present invention also includes configurations that add publicly known technology to the configurations described in the embodiments.

[0292] The following can be derived from the above-described embodiment and modifications.

[0293] The inkjet printing method is a reaction liquid deposition step of ejecting a reaction liquid containing a flocculant and water by an inkjet method and depositing the reaction liquid on the fabric; a colored ink applying step of ejecting a colored ink containing a pigment, water, and a resin that aggregates with the aggregating agent by an inkjet method and applying the ink to the fabric; and At least one of the reaction liquid and the colored ink contains a crosslinking agent; The coating amount of the pigment is 0.12 mg / inch 2 That's all, The amount of crosslinkable functional group applied is 0.05 mol / kg or more.

[0294] The resin in the colored ink aggregates due to the aggregating agent in the reaction liquid, contributing to improved fastness. However, sufficient fastness may not be achieved, especially when each liquid is applied continuously without a drying process. Furthermore, in image areas where the amount of pigment applied is high, dark colors can be expressed, but rub fastness tends to be insufficient. However, with this inkjet printing method, by incorporating a crosslinking agent in at least one of the reaction liquid and the colored ink and setting the amount of crosslinkable functional group applied to 0.05 mol / kg or more, the rub fastness of the resulting image can be improved.

[0295] In the inkjet printing method, The method may further include a transparent ink applying step of ejecting a transparent ink containing water and a resin that aggregates with the aid of the aggregating agent by an inkjet method and applying the ink to the fabric.

[0296] This ink-jet printing method also provides images with excellent abrasion fastness.

[0297] In the inkjet printing method, The reaction liquid and the colored ink may contain a crosslinking agent.

[0298] This ink-jet printing method also provides images with excellent abrasion fastness.

[0299] In the inkjet printing method, When the reaction liquid contains a crosslinking agent, the crosslinking agent may be cationic or nonionic.

[0300] According to this inkjet printing method, even if the reaction liquid contains an aggregating agent, the crosslinking agent in the reaction liquid is cationic or nonionic, so aggregation of the crosslinking agent in the reaction liquid is suppressed, thereby improving storage stability.

[0301] In the inkjet printing method, When the colored ink contains a crosslinking agent, the crosslinking agent may be anionic or nonionic.

[0302] According to this inkjet printing method, even if the colored ink contains a crosslinking agent, the crosslinking agent in the colored ink is anionic or nonionic, so aggregation of the crosslinking agent in the colored ink is suppressed, thereby improving storage stability.

[0303] In the inkjet printing method, At least two of the reaction liquid, the colored ink, and the clear ink may contain a crosslinking agent.

[0304] According to this ink-jet printing method, the rub resistance of the resulting image is further improved.

[0305] In the inkjet printing method, The transparent ink may contain a crosslinking agent.

[0306] According to this ink-jet printing method, the rub resistance of the resulting image is further improved.

[0307] In the inkjet printing method, The reaction liquid, the colored ink, and the clear ink may contain a crosslinking agent.

[0308] According to this ink-jet printing method, the rub resistance of the resulting image is further improved.

[0309] In the inkjet printing method, In the ink-jet printing method, when the transparent ink contains a crosslinking agent, the crosslinking agent is anionic or nonionic.

[0310] According to this inkjet printing method, even if the transparent ink contains a crosslinking agent, the crosslinking agent in the transparent ink is anionic or nonionic, so aggregation of the crosslinking agent in the transparent ink is suppressed, thereby improving storage stability.

[0311] In the inkjet printing method, The time interval between the reaction liquid applying step and the colored ink applying step may be 5 seconds or less.

[0312] According to this inkjet printing method, the time interval between the reaction liquid application step and the colored ink application step is short, so that the colored ink lands before the reaction liquid permeates into the fabric, thereby obtaining an image of better quality.

[0313] In the inkjet printing method, The content of the crosslinking agent in both the reaction liquid and the colored ink may be 10% by mass or less.

[0314] According to this ink-jet printing method, the reaction liquid and the colored ink contain a crosslinking agent in an amount that is not too large, so that the storage stability of each is unlikely to decrease.

[0315] In the inkjet printing method, The content of the crosslinking agent in each of the reaction liquid, the colored ink, and the clear ink may be 15% by mass or less.

[0316] According to this ink-jet printing method, the reaction liquid, the colored ink, and the clear ink contain a crosslinking agent in an amount that is not too large, so that the storage stability of each ink is unlikely to decrease.

[0317] In the inkjet printing method, The content of the crosslinking agent in total of the reaction liquid, the colored ink, and the clear ink may be 5% by mass or more with respect to the total amount of the three liquids.

[0318] According to this ink-jet printing method, the image obtained has better abrasion resistance and color development.

[0319] In the inkjet printing method, The amount of resin applied that is agglomerated by the aggregating agent contained in the colored ink is 0.4 mg / inch 2 It may be more than that.

[0320] This ink-jet printing method provides images with better abrasion resistance.

[0321] In the inkjet printing method, The coating amount of the resin that aggregates due to the aggregating agent contained in the colored ink and the coating amount of the resin that aggregates due to the aggregating agent contained in the transparent ink are 0.4 mg / inch 2 It may be more than that.

[0322] This ink-jet printing method provides images with better abrasion resistance.

[0323] The ink set is a reaction liquid containing a flocculant and water; a colored ink containing a pigment, water, and a resin that aggregates with the aid of the aggregating agent; a transparent ink containing water and a resin that aggregates with the aid of the aggregating agent; Including, at least two of the reaction liquid, the colored ink, and the transparent ink contain a crosslinking agent; The coating amount of the pigment is 0.12 mg / inch 2 That's all, The composition is applied by being ejected by an ink jet method so that the amount of crosslinkable functional group applied is 0.05 mol / kg or more, and is then attached to the fabric.

[0324] With this ink set, at least one of the reaction liquid and the colored ink contains a crosslinking agent, and the amount of crosslinkable functional group applied is 0.05 mol / kg or more, thereby making it possible to obtain images with good abrasion resistance. [Explanation of symbols]

[0325] 1...control unit, 10...medium supply unit, 11...supply shaft unit, 12...bearing unit, 20...medium transport unit, 21...transport roller, 22...transport roller, 23...endless belt, 23a...surface, 23b...inner surface, 24...belt rotation roller, 25...belt drive roller, 26...transport roller, 27...heating unit, 28...transport roller, 29...adhesive, 30...medium recovery unit, 31...winding shaft unit, 32...bearing unit, 40...printing unit, 43...carrier 45...carriage moving part, 45a...guide rail, 45b...guide rail, 46...platen, 50...cleaning unit, 51...cleaning part, 52...pressing part, 53...moving part, 54...cleaning tank, 55...blade, 56...air cylinder, 57...ball bushing, 58...cleaning roller, 60...medium contact part, 61...pressing part, 69...contact part, 90...frame part, 91...belt support part, 95...fabric, 99...floor surface, 100...recording device

Claims

1. a reaction liquid deposition step of ejecting a reaction liquid containing a flocculant and water by an inkjet method and depositing the reaction liquid on the fabric; a colored ink applying step of ejecting a colored ink containing a pigment, water, and a resin that aggregates with the aggregating agent by an inkjet method and applying the ink to the fabric; and At least one of the reaction liquid and the colored ink contains a crosslinking agent; The coating amount of the pigment is 0.12 mg / inch ２ That's all, An ink-jet printing method, wherein the coating amount of the crosslinkable functional group is 0.05 mol / kg or more.

2. In claim 1, The ink-jet printing method further comprises a transparent ink applying step of ejecting a transparent ink containing water and a resin that aggregates with the aid of the aggregating agent by an ink-jet method and applying the ink to the fabric.

3. In claim 1 or claim 2, The ink-jet printing method, wherein the reaction liquid and the colored ink contain a crosslinking agent.

4. In claim 1 or claim 2, The ink-jet printing method, wherein when the reaction liquid contains a crosslinking agent, the crosslinking agent is cationic or nonionic.

5. In claim 1 or claim 2, In the ink-jet printing method, when the colored ink contains a crosslinking agent, the crosslinking agent is anionic or nonionic.

6. In claim 2, an ink-jet printing method, wherein at least two of the reaction liquid, the colored ink, and the transparent ink contain a crosslinking agent;

7. In claim 2, The ink-jet printing method, wherein the transparent ink contains a crosslinking agent.

8. In claim 2, The inkjet printing method, wherein the reaction liquid, the colored ink, and the transparent ink contain a crosslinking agent.

9. In any one of claims 6 to 8, In the ink-jet printing method, when the transparent ink contains a crosslinking agent, the crosslinking agent is anionic or nonionic.

10. In claim 1 or claim 2, an ink-jet printing method, wherein the time interval between the reaction liquid applying step and the colored ink applying step is 5 seconds or less;

11. In claim 1, an ink-jet printing method, wherein the content of the crosslinking agent in each of the reaction liquid and the colored ink is 10% by mass or less;

12. In claim 2, an inkjet printing method, wherein the content of the crosslinking agent in each of the reaction liquid, the colored ink, and the transparent ink is 15% by mass or less;

13. In claim 2, an inkjet printing method, wherein the content of the crosslinking agent in the reaction liquid, the colored ink, and the transparent ink is 5% by mass or more relative to the total amount of the three liquids;

14. In claim 1, The amount of the resin to be aggregated by the aggregating agent contained in the colored ink is 0.4 mg / inch. ２ This is the inkjet printing method.

15. In claim 2, The coating amount of the resin that aggregates due to the aggregating agent contained in the colored ink and the coating amount of the resin that aggregates due to the aggregating agent contained in the transparent ink are 0.4 mg / inch ２ This is the inkjet printing method.

16. a reaction liquid containing a flocculant and water; a colored ink containing a pigment, water, and a resin that aggregates with the aid of the aggregating agent; a transparent ink containing water and a resin that aggregates with the aid of the aggregating agent; Including, at least two of the reaction liquid, the colored ink, and the transparent ink contain a crosslinking agent; The coating amount of the pigment is 0.12 mg / inch ２ That's all, The ink set is used by being ejected by an inkjet method and attached to a fabric so that the coating amount of the crosslinkable functional group is 0.05 mol / kg or more.

Images