Method for manufacturing a dyed or printed article

Abstract

A method for manufacturing a dyed fabric, comprising: a step of applying a treatment liquid containing a coagulant to a cloth by an inkjet method; a step of applying white ink having a charge density of 30 μeq / g or more to the cloth to which the treatment liquid has been applied by a wet-on-wet method using an inkjet method; and a step of applying colored ink having a Young's modulus of 3.0 MPa or less of a dry coating film to the cloth to which the white ink has been applied by a wet-on-wet method using an inkjet method.

Description

Technical Field

[0001] Embodiments of the present invention relate to a method for manufacturing a printed fabric. Background Art

[0002] As methods for printing images such as characters, pictures, and patterns on fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics, in addition to screen printing and roller printing methods, inkjet printing methods have also attracted attention.

[0003] Printed fabrics require fastness.

[0004] Japanese Patent Application Laid-Open No. 2019-99790 describes a printing method for obtaining a printed fabric with excellent rubbing fastness by using an ink composition and a coating composition in which the Young's modulus of the dry coating film is higher than that of the dry coating film of the ink composition.

[0005] Japanese Patent Application Laid-Open No. 2018-131581 describes that by adding a crosslinking agent to an inkjet printing composition, the rubbing fastness of the recorded material tends to be more excellent.

[0006] When printing on a dark-colored fabric or the like by an inkjet printing method, as a method for improving the color development of color ink, for example, there is a method of first printing white ink on the substrate and then printing color ink thereon. Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] An object of an embodiment of the present invention is to provide a printed fabric based on excellent hiding power of white ink and capable of reducing the occurrence of cracking of the ink image after washing.

[0009] Solutions for Solving the Problems

[0010] An embodiment of the present invention relates to a method for manufacturing a printed fabric, which includes: a step of applying a treatment liquid containing a coagulant to a fabric by an inkjet method; a step of applying white ink having a charge density of 30 μeq / g or more to the fabric to which the treatment liquid has been applied by an inkjet method using the wet-on-wet method; and a step of applying color ink having a Young's modulus of 3.0 MPa or less of a dry coating film to the fabric to which the white ink has been applied by an inkjet method using the wet-on-wet method.

[0011] Effects of the Invention

[0012] By an embodiment of the present invention, it is possible to provide a printed fabric based on excellent hiding power of white ink and capable of reducing the occurrence of cracking of the ink image after washing. Detailed Description

[0013] Hereinafter, an embodiment of the present invention will be described in detail. However, the present invention is not limited to these embodiments and can be variously modified and changed.

[0014] A method for manufacturing a dyed fabric according to one embodiment includes: a step of applying a treatment liquid containing a coagulant to the fabric by an inkjet method; a step of applying white ink having a charge density of 30 μeq / g or more to the fabric to which the treatment liquid has been applied by a wet-on-wet method using an inkjet method; and a step of applying colored ink having a Young's modulus of 3.0 MPa or less of a dry coating film to the fabric to which the white ink has been applied by a wet-on-wet method using an inkjet method.

[0015] According to this method for manufacturing a dyed fabric, a dyed fabric having excellent hiding power based on white ink and capable of reducing the occurrence of cracking of the ink image after washing can be provided. Although not limited to theory, the reasons are presumably as follows.

[0016] When applying white ink and colored ink to the fabric to which the treatment liquid has been applied by a wet-on-wet method, the drying steps after applying the treatment liquid and after applying the white ink are not required, which can improve productivity. On the other hand, sometimes the hiding power based on white ink may decrease, or the ink image after washing may easily crack.

[0017] However, when the charge density of the white ink is 30 μeq / g or more, the white ink tends to react more easily with the treatment liquid, whereby the penetration of the white ink into the fabric is easily inhibited, and the hiding power can be improved.

[0018] In addition, in order to improve the hiding power based on white ink, the white ink preferably contains a component that easily reacts with the coagulant of the treatment liquid. However, when the white ink contains such a component, the coating film of the white ink may sometimes become uneven, and the ink image after washing of the obtained dyed fabric may sometimes easily crack. When laminating a layer on the white ink and applying colored ink having a Young's modulus of 3.0 MPa or less of a dry coating film, the ink coating film of the ink image is easily softened. In addition, when the charge density of the white ink is 30 μeq / g or more, the white ink can react sufficiently with the coagulant, so that the colored ink applied after the white ink is less likely to react with the coagulant, and a decrease in the softness of the colored ink coating film can be suppressed. It is considered that this can reduce the generation of cracking of the ink image after washing.

[0019] In the case of the wet-on-wet method, the white ink and the colored ink are mixed, and sometimes the image density of the colored ink may decrease. By this method for manufacturing a dyed fabric, a decrease in the image density of the colored ink can be suppressed. Although not limited to theory, as one of the reasons, it is considered that when the charge density of the white ink is 30 μeq / g or more, components such as pigments and resins in the white ink react with the coagulant of the treatment liquid relatively quickly and coagulate, and the ink thickens, making it difficult to mix with the colored ink.

[0020] Hereinafter, the fabric, the treatment liquid, the white ink, and the colored ink will be described.

[0021] <Fabric>

[0022] As the fabric, natural fibers such as cotton, silk, wool, and hemp can be cited; chemical fibers such as polyester, acrylic, polyurethane, nylon, rayon, cuprammonium fiber, and acetate; or blended fibers thereof. In addition, the fabric can be a woven fabric, a knitted fabric, or a non-woven fabric, etc.

[0023] <Treatment liquid>

[0024] The treatment liquid may contain a flocculant.

[0025] As the flocculant, a component having the function of causing the coloring material in the ink to flocculate on the fabric as the substrate can be used. As the flocculant, for example, metal salts, cationic polymers, organic acids, or combinations thereof can be used. As the metal salt, a polyvalent metal salt is preferably used.

[0026] The content (active ingredient amount) of the flocculant is preferably 1% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more with respect to the total amount of the treatment liquid. The content (active ingredient amount) of the flocculant is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less with respect to the total amount of the treatment liquid. The content (active ingredient amount) of the flocculant is preferably 1 to 50% by mass, more preferably 10 to 45% by mass, and further preferably 15 to 40% by mass with respect to the total amount of the treatment liquid. When two or more flocculants are used, the above-mentioned content of the flocculant is the total content thereof.

[0027] As the metal salt, a polyvalent metal salt can be preferably used.

[0028] The polyvalent metal salt is composed of polyvalent metal ions of divalent or higher and anions. As the polyvalent metal ions of divalent or higher, for example, Ca 2+ , Mg 2+ , Cu 2+ , Ni 2+ , Zn 2+ , Ba 2+ etc. As the anions, for example, Cl - , NO 3 - , CH 3 COO - , I - , Br - , ClO 3 - etc. Specifically, as the polyvalent metal salt, calcium chloride, calcium nitrate, magnesium nitrate, copper nitrate, calcium acetate, magnesium acetate, etc. can be cited.

[0029] These metal salts can be used alone or in combination of two or more.

[0030] The content of the metal salt (active ingredient amount) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more, relative to the total amount of the treatment liquid. On the other hand, the content of the metal salt (active ingredient amount) is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less, relative to the total amount of the treatment liquid. The content of the metal salt (active ingredient amount) is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 40% by mass, relative to the total amount of the treatment liquid. When two or more metal salts are used, the above-mentioned content of the metal salt is the total content thereof.

[0031] It should be noted that when a metal salt hydrate is used as the polyvalent metal salt, the amount of the polyvalent metal salt (active ingredient amount) is converted into the amount of the anhydrous form.

[0032] As the cationic polymer, a cationic water-soluble resin is preferred.

[0033] Examples of the cationic water-soluble resin include polyethylenimine (PEI), polyvinylamine, polyallylamine and its salts, polyvinylpyridine, copolymers of cationic acrylamide, etc. More specifically, for example, polydiallyldimethylammonium chloride can be used.

[0034] Examples of commercially available products of the cationic water-soluble resin include SHALLOL series "SHALLOL DC-303P", "SHALLOL DC-902P", etc. manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., UNISENCE series "UNISENCE FCA1000L", "UNISENCE FPA100L", etc. manufactured by SENKA Corporation, H.C. Polymer series "H.C.Polymer 1S", "H.C.Polymer 1N", "H.C.Polymer 1NS", "H.C.Polymer 2", "H.C.Polymer 2L", etc. (all are trade names) manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0035] In addition, examples of commercially available products of polyethylenimine include EPOMIN series "EPOMIN SP-006", "EPOMIN SP-012", "EPOMIN SP-018", "EPOMIN SP-200", etc. manufactured by Nippon Shokubai Co., Ltd.; "Lupasol FG", "Lupasol G20Waterfree", "Lupasol PR 8515", etc. manufactured by BASF JAPAN LTD. (all are trade names).

[0036] In addition, as commercially available products of polyallylamine, for example, allylamine polymers "PAA-01", "PAA-03", "PAA-05", allylamine polymer hydrochloride polymers "PAA-HCL-01", "PAA-HCL-03", "PAA-HCL-05", allylamine amide sulfate polymers "PAA-SA", etc. (all are trade names) manufactured by Nitto Boseki Co., Ltd. can be cited.

[0037] The cationic polymer may be used alone or in combination of two or more.

[0038] The content (solid content) of the cationic polymer is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 40% by mass with respect to the total amount of the treatment liquid. When two or more cationic polymers are used, the content of the above cationic polymer is the total content thereof.

[0039] Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, malic acid, glycolic acid, thioglycolic acid, lactic acid, malic acid, tartaric acid, citric acid, isocitric acid, gluconic acid, pyruvic acid, oxaloacetic acid, diglycolic acid, benzoic acid, phthalic acid, mandelic acid, salicylic acid, etc. Among them, acetic acid is preferred.

[0040] The organic acid may be used alone or in combination of two or more.

[0041] The content of the organic acid is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 40% by mass with respect to the total amount of the treatment liquid. When two or more organic acids are used, the content of the above organic acid is the total content thereof.

[0042] The treatment liquid preferably contains water as an aqueous solvent.

[0043] There is no particular limitation on the water, and examples thereof include ion-exchanged water, distilled water, ultrapure water, etc.

[0044] The water is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and still more preferably 50 to 80% by mass with respect to the total amount of the treatment liquid.

[0045] The treatment liquid preferably contains a soluble organic solvent.

[0046] As the water-soluble organic solvent, an organic compound that is liquid at room temperature and soluble in water can be used. Preferably, a water-soluble organic solvent that is uniformly mixed with the same volume of water at 20°C under 1 atm is used. For example, lower alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutanol, 2-methyl-2-propanol; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol; glycerols such as glycerol, diglycerol, triglycerol, polyglycerol; glycerol acetates such as monoacetin, diacetin; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether; triethanolamine, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, β-thiodiglycol, sulfolane, etc. The boiling point of the water-soluble organic solvent is preferably 100°C or higher, more preferably 150°C or higher.

[0047] These water-soluble organic solvents can be used alone, or two or more of them can be used in combination as long as they can form a single phase with water. The content of the water-soluble organic solvent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 30% by mass relative to the total amount of the treatment liquid. When two or more water-soluble organic solvents are used, the content of the above-mentioned water-soluble organic solvents is their total content.

[0048] The treatment liquid preferably contains a surfactant. As the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant can be used, and a nonionic surfactant is more preferably used. In addition, a low-molecular surfactant or a high-molecular surfactant can be used.

[0049] The HLB value of the surfactant is preferably 5 to 20, more preferably 10 to 18.

[0050] Examples of the nonionic surfactant include ester surfactants such as glycerol fatty acid esters and sorbitan fatty acid esters; ether surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and polyoxypropylene alkyl ethers; ether ester surfactants such as polyoxyethylene sorbitan fatty acid esters; acetylene surfactants; silicone surfactants; fluorine surfactants, etc. Among them, acetylene glycol-based surfactants and other acetylene surfactants can be preferably used.

[0051] Examples of the acetylene-based surfactant include acetylene glycol-based surfactants, acetylene alcohol-based surfactants, and surfactants having an acetylene group.

[0052] The acetylene glycol-based surfactant is a diol having an acetylene group, preferably a diol having a bilaterally symmetrical structure with the acetylene group located in the center, and may have a structure in which ethylene oxide is added to acetylene glycol.

[0053] Examples of commercially available acetylene surfactants include SURFYNOL series "SURFYNOL 104E", "SURFYNOL 104H", "SURFYNOL 420", "SURFYNOL 440", "SURFYNOL 465", "SURFYNOL 485", etc. manufactured by Evonik Industries AG, and OLFINE series "OLFINE E1004", "OLFINE E1010", "OLFINE E1020", etc. manufactured by Nissin Chemical Industry Co., Ltd. (all trade names).

[0054] Examples of the silicone-based surfactant include polyether-modified silicone-based surfactants, alkyl / aralkyl co-modified silicone-based surfactants, and acrylic silicone-based surfactants.

[0055] Examples of commercially available silicone surfactants include "SILFACE SAG002" and "SILFACE 503A" manufactured by Nissin Chemical Industry Co., Ltd. (all are trade names).

[0056] In addition, examples of other nonionic surfactants include polyoxyethylene alkyl ether surfactants such as Emulgen series "Emulgen 103", "Emulgen 104P", "Emulgen 105", "Emulgen 106", "Emulgen 108", "Emulgen 120", "Emulgen 147", "Emulgen 150", "Emulgen 220", "Emulgen 350", "Emulgen 404", "Emulgen 420", "Emulgen 705", "Emulgen 707", "Emulgen 709", "Emulgen 1108", "Emulgen 4085", and "Emulgen 2025G" manufactured by Kao Corporation (all are trade names).

[0057] Examples of anionic surfactants include, for example, EMAL series products such as "EMAL 0", "EMAL10", "EMAL 2F", "EMAL 40", "EMAL 20C", etc., Neopelex series products such as "Neopelex GS", "Neopelex G-15", "Neopelex G-25", "Neopelex G-65", etc., PELEX series products such as "PELEX OT-P", "PELEX TR", "PELEXCS", "PELEX TA", "PELEX SS-L", "PELEX SS-H", etc., and DEMOL series products such as "DEMOL N, DEMOL NL", "DEMOLRN", "DEMOL MS", etc. (all are trade names) manufactured by Kao Corporation.

[0058] Examples of cationic surfactants include, for example, ACETAMIN series products such as "ACETAMIN24", "ACETAMIN 86", etc., QUARTAMIN series products such as "QUARTAMIN24P", "QUARTAMIN 86P", "QUARTAMIN60W", "QUARTAMIN 86W", etc., and SANISOL series products such as "SANISOL C", "SANISOL B-50", etc. (all are trade names) manufactured by Kao Corporation.

[0059] Examples of amphoteric surfactants include, for example, AMPHITOL series products such as "AMPHITOL20BS", "AMPHITOL 24B", "AMPHITOL 86B", "AMPHITOL20Y-B", "AMPHITOL 20N", etc. (all are trade names) manufactured by Kao Corporation.

[0060] Preferably, one of the above surfactants is used alone, or two or more thereof can be used in combination.

[0061] The content of the surfactant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and further preferably 0.4 to 2% by mass based on the total amount of the treatment liquid. When two or more surfactants are used, the content of the above surfactants is their total content.

[0062] The treatment liquid may further contain other components such as an antifoaming agent, a pH adjuster, an antioxidant, a preservative, etc. as needed.

[0063] The method for manufacturing the treatment liquid is not particularly limited, and it can be appropriately manufactured by a known method. For example, it can be obtained by adding all the components at once or in batches to a stirrer such as a Three-One Motor and dispersing them, and then filtering through a filter such as a membrane filter according to the expectation.

[0064] The charge density of the treatment liquid is preferably 1 to 400 μeq / g, more preferably 10 to 300 μeq / g. Here, the charge density is the charge density measured by the streaming potential method. In addition, the charge density of the treatment liquid is the amount of electric charge per unit amount of active ingredient in the treatment liquid (unit: μeq / g). The amount of active ingredient is the total amount of non-volatile components or solid components contained in the treatment liquid, mainly the amount obtained by removing the solvent from the treatment liquid. Specifically, the treatment liquid is diluted 100-fold with water, and while titrating a 0.0025N polyvinylsulfuric acid potassium (PVSK) solution into the diluted treatment liquid, the reaction end point at which the streaming potential of the diluted treatment liquid becomes 0 V is measured, and the total charge amount of the diluted treatment liquid can be obtained from the amount of PVSK solution used up to this reaction end point. The value obtained by dividing the total charge amount of the diluted treatment liquid by the amount of active ingredient contained in the diluted treatment liquid is the charge density (μeq / g) of the treatment liquid. As the apparatus for measuring the charge density, for example, a colloidal particle charge meter ("Model CAS" manufactured by AFG ANALYTIC GmbH) can be used.

[0065] <White ink>

[0066] As the white ink, those with a charge density of 30 μeq / g or more can be used.

[0067] Here, the charge density is the charge density measured by the streaming potential method. In addition, the charge density of the ink is the amount of electric charge per unit amount of active ingredient in the ink (unit: μeq / g). The amount of active ingredient is the total amount of non-volatile components or solid components contained in the ink, mainly the amount obtained by removing the solvent from the ink. For example, materials such as pigment dispersions, dispersants, and resin emulsions of water-dispersible resins can be used. When they contain solvents, the amount of solvent is also removed to obtain the amount of active ingredient.

[0068] Specifically, the ink is diluted 100-fold with water, and while titrating a 0.0025N poly(diallyldimethylammonium chloride) (polyDADMAC) solution into the diluted ink, the reaction end point at which the streaming potential of the diluted ink becomes 0 V is measured, and the total charge amount of the diluted ink can be obtained from the amount of polyDADMAC solution used up to this reaction end point. The value obtained by dividing the total charge amount of the diluted ink by the amount of active ingredient contained in the diluted ink is the charge density (μeq / g) of the ink.

[0069] As the apparatus for measuring the charge density, for example, a colloidal particle charge meter ("Model CAS" manufactured by AFG ANALYTIC GmbH) can be used.

[0070] The charge density of the white ink is preferably 30 μeq / g or more, more preferably 35 μeq / g or more, and still more preferably 40 μeq / g or more. On the other hand, the charge density of the white ink is preferably 150 μeq / g or less, more preferably 120 μeq / g or less. For example, the charge density of the white ink is more preferably 30 to 150 μeq / g, still more preferably 35 to 150 μeq / g, and still more preferably 40 to 120 μeq / g.

[0071] The adjustment of the charge density of the white ink can be carried out by appropriately selecting the components contained in the white ink. For example, the charge density of the ink can be adjusted by the amount of counterions of the ionic groups of the materials constituting the ink. This amount of counterions represents the amount of ions per unit particle mass. Generally, the more the amount of counterions per unit particle mass, the more likely the charge density is to increase. For example, it is preferable to adjust the charge density by the amount of counterions of the pigment and the water-dispersible resin in the ink. In addition, the charge density of the ink can also be adjusted, for example, by adding ionic components such as a dispersion aid to the ink. In addition, several methods can be combined to adjust the charge density of the ink.

[0072] The white ink preferably contains a coloring material and a resin, for example. As the resin, examples include the polymer dispersant and the water-dispersible resin described later.

[0073] The white ink preferably contains a white pigment as the coloring material.

[0074] Examples of the white pigment include inorganic pigments such as titanium oxide, zinc white, zinc sulfide, antimony oxide, and zirconium oxide. Furthermore, white pigments such as hollow resin fine particles and polymer fine particles can also be used. Among them, from the viewpoint of hiding power, it is preferable to use titanium oxide. The average particle diameter of titanium oxide is preferably 50 nm or more from the viewpoint of hiding power and preferably 500 nm or less from the viewpoint of discharge stability. When using titanium oxide, in order to suppress the photocatalytic effect, it is preferable to use those surface-treated with alumina or silica. The surface treatment amount is preferably 5 to 20% by mass in the pigment.

[0075] As the pigment, the self-dispersible pigment described later can also be blended.

[0076] In addition, a pigment dispersion obtained by previously dispersing a pigment with a pigment dispersant can be used. A pigment dispersion obtained by dispersing with the pigment dispersant described later can be used.

[0077] One kind of coloring material can be used, or two or more kinds can be used in combination.

[0078] The content of the coloring material is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 5 to 15% by mass relative to the total amount of the white ink from the viewpoints of hiding power and the like. When two or more kinds of coloring materials are used, the content of the above-mentioned coloring material is the total content thereof.

[0079] When using white ink in the pigment as the coloring material, in order to stably disperse the pigment in the white ink, a pigment dispersant typified by a polymer dispersant, a surfactant type dispersant, etc. can be used.

[0080] As the polymer dispersant, for example, as commercially available products, there can be mentioned TEGO Dispers series "TEGO Dispers 740W", "TEGO Dispers 750W", "TEGO Dispers 755W", "TEGO Dispers 757W", "TEGO Dispers 760W", etc. manufactured by EVONIK; Solsperse series "Solsperse 20000", "Solsperse 27000", "Solsperse 41000", "Solsperse 41090", "Solsperse 43000", "Solsperse 44000", "Solsperse 46000", etc. manufactured by Lubrizol Corporation; JONCRYL series "JONCRYL 57", "JONCRYL 60", "JONCRYL 62", "JONCRYL 63", "JONCRYL 71", "JONCRYL 501", etc. manufactured by BASF JAPAN LTD.; "DISPERBYK-102", "DISPERBYK-185", "DISPERBYK-190", "DISPERBYK-193", "DISPERBYK-199", etc. manufactured by BYK Japan KK.; "polyvinylpyrrolidone K-30", "polyvinylpyrrolidone K-90", etc. manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (all are trade names).

[0081] Examples of the surfactant-type dispersant include anionic surfactants such as the DEMOL series “DEMOL P”, “DEMOL EP”, “DEMOL N”, “DEMOL RN”, “DEMOL NL”, “DEMOL RN-L”, “DEMOL T-45” etc. manufactured by Kao Corporation, and nonionic surfactants such as the Emulgen series “Emulgen A-60”, “Emulgen A-90”, “Emulgen A-500”, “Emulgen B-40”, “Emulgen L-40”, “Emulgen 420” etc. manufactured by Kao Corporation (all are trade names).

[0082] One kind of the above-mentioned pigment dispersant can be used, or two or more kinds can be used in combination.

[0083] When using the pigment dispersant, the compounding amount in the ink varies depending on its type and is not particularly limited, but generally, based on the mass ratio of the active ingredient (pigment concentration), it is preferably 0.005 to 0.5 relative to 1 of the pigment.

[0084] The white ink preferably contains water as the aqueous solvent, and the main solvent can also be water.

[0085] Water is not particularly limited, and it is preferably as free of ionic components as possible. Especially from the perspective of the storage stability of the ink, it is preferred that the content of polyvalent metal ions such as calcium is low. As water, for example, ion-exchanged water, distilled water, ultrapure water, etc. can be used.

[0086] Regarding water, from the perspective of adjusting the ink viscosity, it is preferably contained in an amount of 30 to 90% by mass, more preferably 40 to 85% by mass, and further preferably 50 to 80% by mass relative to the total amount of the white ink.

[0087] The white ink can contain a water-soluble organic solvent.

[0088] As the water-soluble organic solvent, an organic compound that is liquid at room temperature and soluble in water can be used. It is preferred to use a water-soluble organic solvent that is uniformly mixed with the same volume of water at 1 atm and 20°C.

[0089] As the water-soluble organic solvent, for example, those described in the above treatment liquid can be selected and used.

[0090] These water-soluble organic solvents can be used alone, or two or more kinds can be used in combination as long as they can form a single phase with water.

[0091] The content of the water-soluble organic solvent is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass relative to the total amount of the white ink. When two or more water-soluble organic solvents are used, the content of the above-mentioned water-soluble organic solvents is their total content.

[0092] The white ink preferably contains a surfactant.

[0093] As the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant can be used, and a nonionic surfactant is more preferable. In addition, a low-molecular surfactant or a high-molecular surfactant can be used.

[0094] The HLB value of the surfactant is preferably 5 to 20, and more preferably 10 to 18.

[0095] As the surfactant, for example, those described in the above treatment liquid can be selected and used.

[0096] Among them, an acetylene-based surfactant such as an acetylene glycol-based surfactant can be preferably used.

[0097] One kind of surfactant can be used, or two or more kinds can be used in combination.

[0098] The content of the surfactant is preferably 0.1 to 5% by mass, and more preferably 0.2 to 2% by mass relative to the total amount of the white ink. When two or more surfactants are used, the content of the above-mentioned surfactants is their total content.

[0099] The white ink may further contain a water-dispersible resin.

[0100] When the water-dispersible resin is contained, a good reaction between the coagulant of the treatment liquid and the white ink is easily obtained, and a good covering power based on the white ink is easily obtained.

[0101] The water-dispersible resin is preferably resin particles that can be dispersed in an aqueous solvent. The water-dispersible resin can be incorporated into the ink in the form of an oil-in-water type resin emulsion, for example.

[0102] In order to be stably dispersed in water, the water-dispersible resin can be a self-emulsifying type into which a hydrophilic component is introduced, or can be made water-dispersible by using an external emulsifier.

[0103] From the viewpoint of inkjet ejection property, the average particle diameter of the water-dispersible resin is preferably 300 nm or less, more preferably 200 nm or less, and still more preferably 150 nm or less. For example, the average particle diameter of the water-dispersible resin is preferably in the range of 10 nm to 300 nm. Here, the average particle diameter of the water-dispersible resin is the average particle diameter based on volume and is a value measured by the light scattering method.

[0104] As the type of the water-dispersible resin, a resin that forms a transparent coating film is preferably used.

[0105] Examples of the water-dispersible resin include conjugated diene resins such as styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, and vinyl chloride-vinyl acetate copolymer; acrylic resins such as polymers of acrylate and methacrylate, or copolymers thereof with styrene, etc.; vinyl-based resins such as ethylene-vinyl acetate copolymer, or functional group-modified resins of these various resins based on monomers containing functional groups such as carboxyl group; water-dispersible resins such as melamine resin, urea resin, polyurethane resin, unsaturated polyester resin, polyolefin resin, silicone resin, polyvinyl butyral resin, and alkyd resin. Resin emulsions of these individual resins can be used, or a mixed-type resin emulsion can also be used.

[0106] The water-dispersible resin can be anionic, cationic, nonionic, or amphoteric. As the water-dispersible resin, an anionic water-dispersible resin is preferred.

[0107] As the anionic water-dispersible resin, it can be, for example, a self-emulsifying type resin in which an anionic group possessed by the resin exists on the particle surface, or it can be a resin particle surface to which an anionic dispersant or the like has been attached and surface-treated. Representative anionic groups include carboxyl group, sulfo group, phosphoric acid group, etc. Examples of the anionic dispersant are anionic surfactants, etc.

[0108] The white ink preferably contains water-dispersible resin A and water-dispersible resin B having different charge densities from each other. It is considered that among water-dispersible resin A and water-dispersible resin B, when the one with a lower charge density is water-dispersible resin A and the one with a higher charge density is water-dispersible resin B, after the water-dispersible resin B with a higher charge density forms a coating film, the water-dispersible resin A with a lower charge density forms a coating film in a manner of filling the unevenness of the coating film of the water-dispersible resin B, whereby the cracking of the ink image after washing can be further reduced.

[0109] The charge density of the water-dispersible resin A is preferably 60 μeq / g or less, more preferably 55 μeq / g or less, and still more preferably 50 μeq / g or less. The charge density of the water-dispersible resin B is preferably 65 μeq / g or more, preferably 70 μeq / g or more, and preferably 75 μeq / g or more. In one embodiment, the white ink preferably contains: water-dispersible resin A with a charge density of 60 μeq / g or less, 55 μeq / g or less, or 50 μeq / g or less, and water-dispersible resin B with a charge density of 65 μeq / g or more, 70 μeq / g or more, or 75 μeq / g or more. For example, the white ink preferably contains: water-dispersible resin A with a charge density of 55 μeq / g or less, and water-dispersible resin B with a charge density of 75 μeq / g or more.

[0110] The water-dispersible resin A and the water-dispersible resin B are not particularly limited, and can be independently selected from the above-mentioned resins and the like. The water-dispersible resin A and the water-dispersible resin B are each preferably an anionic water-dispersible resin.

[0111] The mass ratio (water-dispersible resin A: water-dispersible resin B) of the contents (solid components) of the water-dispersible resin A and the water-dispersible resin B is preferably 2:1 to 2:3.

[0112] Here, the charge density of the water-dispersible resin is the charge density measured by the streaming potential method. In addition, the charge density of the water-dispersible resin is the amount of electric charge per unit amount of effective component of the water-dispersible resin (unit: μeq / g). Specifically, a resin emulsion of the water-dispersible resin is diluted with water so that the solid component becomes 0.05% by mass to prepare a dilution solution. While titrating a 0.0025N poly(diallyldimethylammonium chloride) (polyDADMAC) solution into the dilution solution, the reaction end point at which the streaming potential of the dilution solution becomes 0 V is measured, and the total charge amount of the dilution solution can be obtained from the amount of polyDADMAC solution used up to this reaction end point. The value obtained by dividing the total charge amount of the dilution solution by the amount of solid component contained in the dilution solution is the charge density (μeq / g) of the water-dispersible resin.

[0113] As the apparatus for measuring the charge density, for example, a colloidal particle charge meter (“Model CAS” manufactured by AFG ANALYTIC GmbH) can be used.

[0114] Examples of commercially available products of the water-dispersible resin include “SUPERFLEX460” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “UW-1005D-C1” and “UW-1527DF” manufactured by Ube Industries, Ltd., “DAOTANTW6490 / 35WA”, “DAOTAN TW6460 / 35WA”, “DAOTAN TW6490 / 30WA” manufactured by Daicel-Allnex Ltd., “NeoRez R986” manufactured by Covestro AG, “Mowinyl 6763” manufactured by Japan Coating Resin co.,ltd., “ADEKA BONTIGHTER HUX-370” manufactured by ADEKA Corporation, etc. (all are trade names).

[0115] These water-dispersible resins can be used alone or in combination of two or more. The content (solid content) of the water-dispersible resin is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more relative to the total amount of white ink. The content (solid content) of the water-dispersible resin is preferably 30% by mass or less, more preferably 20% by mass or less relative to the total amount of white ink. The content (solid content) of the water-dispersible resin is preferably 1 to 30% by mass, more preferably 3 to 30% by mass, and further preferably 5 to 20% by mass relative to the total amount of white ink. When using two or more water-dispersible resins, the content of the above-mentioned water-dispersible resin is its total content.

[0116] The content (solid content) of the water-dispersible resin in the white ink is preferably 0.1 to 10, more preferably 1 to 5, in terms of mass ratio, relative to the content of the pigment in the white ink. When two or more water-dispersible resins are used, the content of the water-dispersible resins is the total content. The same applies to the content of the pigment.

[0117] The white ink may contain other components as appropriate. Examples of other components include a pH adjuster and a preservative.

[0118] The method for producing white ink is not particularly limited, and the white ink can be produced appropriately by a known method. For example, all components can be put into a stirrer such as a Three-One Motor at once or in batches to disperse the components, and the ink can be obtained by passing the mixture through a filter such as a membrane filter as desired.

[0119] White ink can be made into water-based printing and dyeing inkjet ink for use.

[0120] The pH of the white ink is preferably 7.0 to 10.0, and more preferably 7.5 to 9.0, from the viewpoint of storage stability of the ink.

[0121] The viscosity of the white ink can be adjusted appropriately. For example, from the viewpoint of dischargeability, the viscosity at 23° C. is preferably 1 to 30 mPa·s.

[0122] <Color Ink>

[0123] As the color ink, a color ink having a Young's modulus of a dry coating film of 3.0 MPa or less can be used.

[0124] Here, the dry coating film of the color ink refers to: after the color ink is diluted with ion exchange water in such a manner that the total solid content of the pigment and resin in the color ink becomes 20 mass%, the diluted solution is poured into a PTFE (polytetrafluoroethylene) culture dish in such a manner that the film thickness after drying becomes 0.4 mm, and the dry coating film is obtained by heating and drying at 70°C for 60 minutes, at 120°C for 20 minutes, and at 160°C for 10 minutes in a constant temperature bath.

[0125] The Young's modulus of the dried coating film can be measured using a test piece obtained by cutting the dried coating film into a dumbbell No. 8 shape specified in JIS K6251. Specifically, using a TENSILON universal testing machine (manufactured by A&D Company, Ltd., "RTG-1250" (trade name)), the stress-strain (elongation rate) curve of the test piece is measured under the conditions of a tensile speed of 500 mm / minute and a distance between chucks of 20 mm. The stress at an elongation rate of 10% of the obtained stress-strain curve is taken as the Young's modulus [MPa] of the test piece. It should be noted that the film thickness of the dried coating film can be determined by actual measurement based on a micrometer (manufactured by Mitutoyo Corporation, "MDH-25PX" (trade name)).

[0126] The Young's modulus of the dried coating film of the color ink can be prepared by adjusting the types and amounts of the components in the color ink. For example, it can be adjusted by adjusting the Young's modulus of resins such as water-dispersible resins in the color ink, the content of resins such as water-dispersible resins in the color ink, the mass ratio of pigments to water-dispersible resins in the color ink, etc. The Young's modulus of the dried coating film of the color ink can also be adjusted by combining several methods.

[0127] The Young's modulus of the dried coating film of the color ink is preferably 3.0 MPa or less, more preferably 2.0 MPa or less, and further preferably 1.0 MPa or less. The Young's modulus of the dried coating film of the color ink is preferably 0.1 MPa or more, more preferably 0.3 MPa or more. For example, the Young's modulus of the dried coating film of the color ink is preferably 0.1 - 3.0 MPa, more preferably 0.3 - 2.0 MPa, and further preferably 0.3 - 1.0 MPa.

[0128] Examples of the color ink include inks other than white ink such as magenta ink, cyan ink, yellow ink, and black ink.

[0129] The color ink preferably contains, for example, a coloring material and a resin. Examples of the resin include, for example, the polymer dispersant and water-dispersible resin described later.

[0130] In the color ink, as the coloring material, it may contain a pigment, a dye, or a combination thereof, and preferably contains a pigment.

[0131] As the pigment, it preferably contains a non-white pigment.

[0132] As non-white pigments, organic pigments such as azo pigments, phthalocyanine pigments, polycyclic pigments, and dye lakes, and inorganic pigments such as carbon black and metal oxides can be used. As azo pigments, soluble azo lake pigments, insoluble azo pigments, and condensed azo pigments can be cited. As phthalocyanine pigments, metal phthalocyanine pigments and metal-free phthalocyanine pigments can be cited. As polycyclic pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindoline pigments, isoindolinone pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, and diketopyrrolopyrrole (DPP) can be cited. As carbon black, furnace black, lamp black, acetylene black, channel black, etc. can be cited. As metal oxides, titanium oxide, zinc oxide, etc. can be cited. These pigments can be used alone or in combination of two or more.

[0133] From the viewpoints of ejection stability and storage stability, the average particle diameter of the pigment particles in the ink, in terms of the average value based on volume in the particle size distribution measured by the dynamic light scattering method, is preferably 300 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less.

[0134] Self-dispersing pigments can also be blended as pigments. Self-dispersing pigments are pigments in which hydrophilic functional groups are introduced onto the surface of the pigments by chemical treatment or physical treatment. As the hydrophilic functional groups introduced into the self-dispersing pigments, those having ionic properties are preferred. By making the pigment surface negatively or positively charged, the pigment particles can be stably dispersed in water by electrostatic repulsion. As the anionic functional groups, sulfonic acid groups, carboxyl groups, carbonyl groups, hydroxyl groups, phosphonic acid groups, etc. are preferred. As the cationic functional groups, quaternary ammonium groups, quaternary phosphonium groups, etc. are preferred.

[0135] These hydrophilic functional groups can be directly bonded to the pigment surface or bonded through other atomic groups. As the other atomic groups, alkylene groups, phenylene groups, naphthylene groups, etc. can be cited, but are not limited to these. As the treatment methods for the pigment surface, diazotization treatment, sulfonation treatment, hypochlorous acid treatment, humic acid treatment, vacuum plasma treatment, etc. can be cited.

[0136] As self-dispersing pigments, for example, it is preferable to use "CAB-O-JET200", "CAB-O-JET300", "CAB-O-JET250C", "CAB-O-JET260M", "CAB-O-JET270", "CAB-O-JET450C", etc. of the CAB-O-JET series manufactured by Cabot Corporation, "BONJET BLACK CW-1", "BONJET BLACK CW-2", "BONJET BLACK CW-3", "BONJET BLACK CW-4", etc. (all are trade names) manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.

[0137] As pigments, microencapsulated pigments in which the pigments are covered with resin can be used.

[0138] Pigment dispersions in which pigments are pre-dispersed with a pigment dispersant can be used. As commercially available products of pigment dispersions dispersed with a pigment dispersant, for example, the HOSTAJET series manufactured by Clariant Corporation, the FUJI SP series manufactured by Fuji Pigment Co., Ltd., etc. can be cited. Pigment dispersions dispersed with the pigment dispersant described later can be used.

[0139] As dyes, water-soluble dyes such as basic dyes, acid dyes, direct dyes, soluble vat dyes, acid mordant dyes, mordant dyes, reactive dyes, vat dyes, sulfur dyes, etc. and water-soluble dyes that become water-soluble through reduction, etc. can be preferably used. In addition, disperse dyes such as azo-based, anthraquinone-based, azomethine-based, nitro-based, etc. can be preferably used. These can be used alone or in combination of multiple kinds.

[0140] One kind of coloring material can be used, or two or more kinds can be used in combination.

[0141] From the viewpoints of printing density and ink viscosity, the content of the coloring material is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 2 to 7% by mass relative to the total amount of the color ink. When two or more kinds of coloring materials are used, the content of the above-mentioned coloring material is the total content thereof.

[0142] As the coloring material, when using a color ink with pigments, in order to stably disperse the pigments in the color ink, pigment dispersants typified by polymer dispersants, surfactant-type dispersants, etc. can be used.

[0143] As the pigment dispersant, for example, those described in the above white ink can be selected and used.

[0144] The compounding amount in the colored ink when using a pigment dispersant varies depending on its type and is not particularly limited. Generally, based on the mass ratio of the active ingredient (pigment concentration), it is preferably 0.005 to 0.5 relative to 1 of the pigment.

[0145] The colored ink preferably contains water as an aqueous solvent, and the main solvent can also be water.

[0146] Water is not particularly limited, and it is preferably as free of ionic components as possible. Especially from the viewpoint of the storage stability of the ink, it is preferred that the content of polyvalent metal ions such as calcium is low. As water, for example, ion-exchanged water, distilled water, ultrapure water, etc. can be used.

[0147] Regarding water, from the viewpoint of adjusting the ink viscosity, it is preferably contained in an amount of 20% to 80% by mass, more preferably 30% to 70% by mass, relative to the total amount of the colored ink.

[0148] The colored ink may contain a water-soluble organic solvent. As the water-soluble organic solvent, an organic compound that is liquid at room temperature and soluble in water can be used, and a water-soluble organic solvent that is uniformly mixed with the same volume of water at 1 atm and 20 °C is preferably used.

[0149] As the water-soluble organic solvent, for example, those described in the above treatment liquid can be selected and used.

[0150] These water-soluble organic solvents can be used alone, and as long as they can form a single phase with water, two or more kinds can also be used in combination.

[0151] Regarding the content of the water-soluble organic solvent in the colored ink, it is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, relative to the total amount of the colored ink. When two or more water-soluble organic solvents are used, the content of the above water-soluble organic solvents is their total content.

[0152] The colored ink preferably contains a surfactant.

[0153] As the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant can be used, and a nonionic surfactant is preferred. In addition, a low-molecular surfactant or a high-molecular surfactant can also be used.

[0154] The HLB value of the surfactant is preferably 5 to 20, more preferably 10 to 18.

[0155] As the surfactant, for example, those described in the above treatment liquid can be selected and used. Among them, acetylene-based surfactants such as acetylene glycol-based surfactants can be preferably used.

[0156] One kind of surfactant can be used, or two or more kinds can be used in combination.

[0157] The content of the surfactant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, relative to the total amount of the color ink. When two or more surfactants are used, the content of the above surfactants is the total content thereof.

[0158] The color ink may contain a water-dispersible resin.

[0159] The water-dispersible resin is preferably resin particles that can be dispersed in an aqueous solvent. The water-dispersible resin can be blended in the ink in the form of an oil-in-water type resin emulsion, for example.

[0160] The water-dispersible resin may be a self-emulsifying type into which a hydrophilic component is introduced for stable dispersion in water, or may be made water-dispersible by using an external emulsifier.

[0161] From the viewpoint of inkjet ejection property, the average particle diameter of the water-dispersible resin is preferably 300 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less. For example, the average particle diameter of the water-dispersible resin is preferably in the range of 10 nm to 300 nm. Here, the average particle diameter of the resin is the average particle diameter based on volume and is a value measured by the light scattering method.

[0162] As the type of the water-dispersible resin, a resin that forms a transparent coating film is preferably used.

[0163] As the water-dispersible resin, for example, those described in the above white ink can be selected and used.

[0164] The water-dispersible resin can be anionic, cationic, nonionic, or amphoteric. As the water-dispersible resin, an anionic water-dispersible resin is preferred.

[0165] As the anionic water-dispersible resin, it may be a resin in which an anionic group existing in the resin is present on the particle surface like a self-emulsifying type resin, or may be a resin particle surface-treated with an anionic dispersant or the like. Representative anionic groups are carboxyl group, sulfonic group, phosphoric group, etc. Anionic dispersants are, for example, anionic surfactants, etc.

[0166] These water-dispersible resins can be used alone or in combination of two or more. The content of the water-dispersible resin (solid content) is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more, relative to the total amount of the color ink. The content of the water-dispersible resin (solid content) is preferably 30% by mass or less, more preferably 20% by mass or less, relative to the total amount of the color ink. The content of the water-dispersible resin (solid content) is preferably 1 to 30% by mass, more preferably 3 to 30% by mass, and further preferably 5 to 20% by mass, relative to the total amount of the color ink. When two or more water-dispersible resins are used, the content of the above-mentioned water-dispersible resin is the total content thereof.

[0167] The color ink preferably contains a pigment and a water-dispersible resin.

[0168] When the color ink contains a pigment and a water-dispersible resin, the ratio of the contents of the pigment and the water-dispersible resin is not particularly limited. From the viewpoint of more effectively suppressing the cracking of the ink image after washing, in the color ink, the mass ratio of the water-dispersible resin to the pigment (water-dispersible resin / pigment) is preferably 2.5 or more. On the other hand, from the viewpoint of dischargeability, in the color ink, the mass ratio of the water-dispersible resin to the pigment (water-dispersible resin / pigment) is preferably 5.0 or less, more preferably 4.0 or less. In the color ink, the mass ratio of the water-dispersible resin to the pigment (water-dispersible resin / pigment) is preferably 2.5 to 5.0, more preferably 2.5 to 4.0. When two or more water-dispersible resins are used, the content of the water-dispersible resin in the above-mentioned mass ratio of the water-dispersible resin to the pigment is the total content thereof, and the same applies to the content of the pigment.

[0169] The color ink preferably contains a crosslinking agent. When a crosslinking agent is contained, the film of the color ink becomes stronger, and the cracking of the ink image after washing tends to be further suppressed. In addition, the image density of the color ink can be more easily increased.

[0170] Examples of the crosslinking agent include carbodiimide compounds, isocyanate compounds, oxazoline compounds, and the like.

[0171] Examples of commercially available products of carbodiimide compounds include "Carbodilite V-02" manufactured by Nisshinbo Chemical Inc. Examples of commercially available products of oxazoline compounds include "Epocross K2030E" manufactured by Nippon Shokubai Co., Ltd. Examples of commercially available products of isocyanate compounds include "Elastron BN69" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0172] The crosslinking agent can be used alone or in combination of two or more kinds. The content of the crosslinking agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, relative to the total amount of the color ink. The content of the crosslinking agent is preferably 5% by mass or less, more preferably 2% by mass or less, relative to the total amount of the color ink. The content of the crosslinking agent is preferably 0.1 to 5% by mass, more preferably 0.2 to 2% by mass, relative to the total amount of the color ink. When two or more crosslinking agents are used, the content of the crosslinking agent described above is the total content thereof.

[0173] The color ink may also appropriately contain other components. Examples of other components include pH adjusters, preservatives, etc.

[0174] The method for producing the color ink is not particularly limited, and it can be appropriately produced using a known method. For example, all components can be put into a mixer such as a Three-One Motor at once or in batches and dispersed, and the ink can be obtained through a filter such as a membrane filter as desired.

[0175] The color ink can be used as an aqueous printing and dyeing inkjet ink.

[0176] From the viewpoint of the storage stability of the ink, the pH of the color ink is preferably 7.0 to 10.0, more preferably 7.5 to 9.0.

[0177] The viscosity of the color ink can be appropriately adjusted. For example, from the viewpoint of dischargeability, the viscosity at 23°C is preferably 1 to 30 mPa·s.

[0178] <Method for manufacturing a printed and dyed article>

[0179] A method for manufacturing a printed and dyed article according to one embodiment may include: a step of applying the above-mentioned treatment liquid to a cloth by an inkjet method; a step of applying the above-mentioned white ink to the cloth to which the treatment liquid has been applied by a wet-on-wet method by an inkjet method; and a step of applying the above-mentioned color ink to the cloth to which the white ink has been applied by a wet-on-wet method by an inkjet method.

[0180] The treatment liquid, the white ink, and the color ink are preferably applied to the cloth by an inkjet method respectively. The inkjet method is a printing method that is non-contact with the substrate and can easily and freely form an image as needed.

[0181] The inkjet method is not particularly limited, and any method such as a piezoelectric method, an electrostatic method, or a thermal method can be used. When using an inkjet printing apparatus, it is preferable to discharge droplets of the treatment liquid or the ink from an inkjet head based on a digital signal and attach the discharged droplets to the cloth.

[0182] The step of applying the treatment liquid to the cloth by an inkjet method will be described.

[0183] The area to which the treatment liquid is applied may be an area having the same shape as the white-ink-based image, a wider area including the shape of the white-ink-based image, or the entire surface of the fabric.

[0184] The area to which the treatment liquid is applied, the area to which the white ink is applied, and the area to which the color ink is applied preferably at least partially overlap.

[0185] The application amount of the treatment liquid to the fabric is preferably 5 to 200 g / m 2 , preferably 10 to 100 g / m 2 , more preferably 15 to 80 g / m 2 .

[0186] A process of applying white ink to the fabric to which the treatment liquid has been applied by wet-on-wet method using an inkjet method will be described.

[0187] The area to which the white ink is applied may be an area having the same shape as the color-ink-based image; a wider area including the shape of the color-ink-based image; or the entire surface of the fabric.

[0188] The white ink is preferably applied in such a manner that the applied area at least partially overlaps with the area to which the treatment liquid is applied. Preferably, the area to which the treatment liquid is applied, the area to which the white ink is applied, and the area to which the color ink is applied at least partially overlap.

[0189] The white ink is preferably applied to the fabric to which the treatment liquid has been applied by wet-on-wet method. The white ink is preferably applied in a state where the moisture is not completely removed from the fabric to which the treatment liquid has been applied. Preferably, the white ink can be applied in a state where the fabric to which the treatment liquid has been applied remains in a wet state. For example, preferably, after applying the treatment liquid to the fabric, the white ink is applied to the fabric without performing a drying process such as heating and drying. The temperature of the surface of the fabric from when the treatment liquid is applied until the white ink is applied is preferably 40°C or lower, more preferably 35°C or lower. After applying the treatment liquid, the white ink is preferably applied in a state where the residual amount of the volatile component of the treatment liquid on the fabric is 90% by mass or more. The time from when the treatment liquid is applied to the fabric until the white ink is applied is preferably 0.1 to 200 seconds.

[0190] The application amount of the white ink to the fabric is not particularly limited. For example, it is preferably 80 to 400 g / m 2 , more preferably 120 to 250 g / m 2 .

[0191] A process of applying color ink to the fabric to which the white ink has been applied by wet-on-wet method using an inkjet method will be described.

[0192] The color ink is preferably applied in such a manner that the applied area at least partially overlaps with the area to which the white ink is applied. Preferably, the area to which the treatment liquid is applied, the area to which the white ink is applied, and the area to which the color ink is applied at least partially overlap.

[0193] The color ink is preferably applied to the cloth to which the white ink has been applied by the wet-on-wet method. The color ink is preferably applied in a state where the moisture is not completely removed from the cloth to which the white ink has been applied. Preferably, the color ink can be applied in a state where the cloth to which the white ink has been applied remains in a wet state. For example, it is preferred that after applying the white ink to the cloth, the color ink is applied to the cloth without performing a drying process such as heat drying. The temperature of the surface of the cloth from when the white ink is applied until the color ink is applied is preferably 40 °C or lower, more preferably 35 °C or lower. After applying the white ink, the color ink is preferably applied in a state where the residual amount of the volatile component of the white ink on the cloth is 90% by mass or more. The time from when the white ink is applied to the cloth until the color ink is applied is preferably 0.1 to 200 seconds.

[0194] There is no particular limitation on the amount of the color ink applied to the cloth. For example, it is preferably 1 to 100 g / m 2 , more preferably 5 to 50 g / m 2 .

[0195] It should be noted that one type of color ink can be applied, or two or more types of color ink can be applied.

[0196] The process of applying the treatment liquid, the process of applying the white ink, and the process of applying the color ink can be carried out using separate printing apparatuses for each, or can be carried out using one printing apparatus. For example, two printing apparatuses can be used, and one of the printing apparatuses can be used to carry out the process of applying the treatment liquid, and the other can be used to carry out the process of applying the white ink and the process of applying the color ink.

[0197] In the method for manufacturing a printed fabric, it is preferred to provide a process of heat-treating the cloth after applying the color ink.

[0198] The heat treatment temperature can be appropriately selected according to the material of the cloth, etc. The heat treatment temperature is, for example, preferably 100 °C or higher, more preferably 150 °C or higher. From the viewpoint of reducing damage to the cloth, the heat treatment temperature is preferably 200 °C or lower.

[0199] There is no particular limitation on the heating device. For example, a hot press, a roll heater, a warm air device, an infrared lamp heater, etc. can be used.

[0200] The heat treatment time can be appropriately set according to the heating method, etc. For example, it is preferably 1 second to 10 minutes, and can be 5 seconds to 5 minutes.

[0201] After applying the color ink to the cloth, a process of applying a post-treatment liquid can also be provided. After applying the color ink, a process of heating the cloth can be provided, and then the post-treatment liquid can be applied. The post-treatment liquid can also be applied by the wet-on-wet method after applying the color ink. Furthermore, after applying the post-treatment liquid, a process of heating the cloth can also be provided.

[0202] <Set of inks>

[0203] Using one embodiment, there is provided an ink set for printing and dyeing by inkjet, which contains: a treatment liquid containing a coagulant, a white ink having a charge density of 30 μeq / g or more, and a color ink having a Young's modulus of the dried coating film of 3.0 MPa or less.

[0204] As the treatment liquid, white ink, and color ink, the treatment liquid, white ink, and color ink that can be used in the above-described method for manufacturing a printed and dyed product can be used, respectively.

[0205] The ink set for printing and dyeing by inkjet may further contain a post-treatment liquid or the like.

[0206] Examples

[0207] Hereinafter, the present invention will be described in detail using examples. The present invention is not limited to the following examples.

[0208] <Manufacture of treatment liquid>

[0209] The formulation of treatment liquid U-1 is shown in Table 1. The raw materials described in Table 1 were mixed in the mixing ratios shown in Table 1, and coarse particles were removed using a membrane filter with a pore size of 3 μm to obtain treatment liquid U-1.

[0210] [Table 1]

[0211]

[0212] The details of the materials described in Table 1 are shown below.

[0213] (Coagulant)

[0214] Calcium chloride: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., active ingredient 100% by mass

[0215] (Water-soluble organic solvent)

[0216] 1,4-Butanediol: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0217] (Surfactant)

[0218] OLFINE E1010: acetylene-based surfactant, manufactured by Nissin Chemical Industry Co., Ltd., active ingredient 100% by mass

[0219] <Manufacture of white ink>

[0220] The formulations of white inks W-1 to W-8 are shown in Tables 2 and 3. For the mixing ratios of the raw materials in Tables 2 and 3, when the materials contain solvents and the like, the amounts including them are used.

[0221] According to the mixing ratios shown in Tables 2 and 3, the respective materials described in Tables 2 and 3 were mixed, and coarse particles were removed using a membrane filter with a pore size of 3 μm to obtain white ink.

[0222] [Table 2]

[0223]

[0224] [Table 3]

[0225]

[0226] The details of the materials described in Tables 2 and 3 are shown below.

[0227] (Pigment dispersion)

[0228] White pigment dispersion: Obtained by the following method, the pigment component is 40% by mass

[0229] (Water-dispersible resin)

[0230] DAOTAN TW6490 / 35WA: Water-dispersible polyurethane resin (aqueous resin emulsion), manufactured by Daicel-Allnex Ltd., solid content 35% by mass

[0231] DAOTAN TW6460 / 35WA: Water-dispersible polyurethane resin (aqueous resin emulsion), manufactured by Daicel-Allnex Ltd., solid content 35% by mass

[0232] DAOTAN TW6450 / 30WA: Water-dispersible polyurethane resin (aqueous resin emulsion), manufactured by Daicel-Allnex Ltd., solid content 30% by mass

[0233] NeoRez R986: Water-dispersible polyurethane resin (aqueous resin emulsion), manufactured by Covestro AG, solid content 25% by mass

[0234] Mowinyl 6763: Water-dispersible polyurethane resin (aqueous resin emulsion), manufactured by Japan Coating Resinco.,ltd., solid content 35% by mass

[0235] (Water-soluble organic solvent)

[0236] 1,4-Butanediol: Manufactured by Fujifilm Wako Pure Chemical Corporation

[0237] (Surfactant)

[0238] OLFINE E1010: Acetylene-based surfactant, manufactured by Nissin Chemical Industry Co., Ltd., active ingredient 100% by mass

[0239] <Manufacture of white pigment dispersion>

[0240] 400 g of titanium oxide “R-21N” (manufactured by Sakai Chemical Industry Co., Ltd.) as a white pigment, 20 g (5 g in terms of active ingredient) of “DEMOL EP” (manufactured by Kao Corporation) as a pigment dispersant, and 580 g of ion-exchanged water were mixed, and using a bead mill (manufactured by SHINMARU ENTERPRISES CORPORATION, DYNO-MILL KDL Type A), zirconia beads with a diameter of 0.5 mm were dispersed at a filling rate of 80% and a residence time of 5 minutes to obtain a white pigment dispersion (pigment component: 40% by mass).

[0241] <Manufacture of Color Ink>

[0242] Tables 4 and 5 show the formulations of color inks K-1 to K-12. For the mixing ratios of the raw materials in the tables, when the materials contain solvents, etc., the amounts including them are used.

[0243] According to the mixing ratios shown in Tables 4 and 5, the respective materials described in Tables 4 and 5 were mixed, and coarse particles were removed using a membrane filter with a pore size of 3 μm to obtain color ink.

[0244] [Table 4]

[0245]

[0246] [Table 5]

[0247]

[0248] Details of the materials described in Tables 4 and 5 are shown below.

[0249] (Pigment Dispersion)

[0250] Black pigment dispersion: Obtained by the following method, pigment component: 20% by mass

[0251] (Water-Dispersible Resin)

[0252] SUPERFLEX 460: Water-dispersible polyurethane resin (aqueous resin emulsion), manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., solid content: 38% by mass

[0253] UW-1005D-C1: Water-dispersible polyurethane resin (aqueous resin emulsion), manufactured by Ube Industries, Ltd., solid content: 30% by mass

[0254] UW-1527DF: Water-dispersible polyurethane resin (aqueous resin emulsion), manufactured by Ube Industries, Ltd., solid content: 30% by mass

[0255] ADEKA BONTIGHTER HUX-370: A water-dispersible acrylic resin (aqueous resin emulsion), manufactured by ADEKA CORPORATION, 33% by mass

[0256] (Crosslinking agent)

[0257] Carbodilite V-02: A carbodiimide compound, manufactured by Nisshinbo Chemical Inc., 40% by mass of solid content

[0258] Elastron BN69: An isocyanate compound, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 40% by mass of solid content

[0259] Epocross K2030E: An oxazoline compound, manufactured by Nippon Shokubai Co., Ltd., 40% by mass of solid content

[0260] (Surfactant)

[0261] OLFINE E1010: An acetylene-based surfactant, manufactured by Nisshin Chemical Industry Co., Ltd., 100% by mass of active ingredient

[0262] (Water-soluble organic solvent)

[0263] 1,4-Butanediol: Manufactured by FUJIFILM Wako Pure Chemical Corporation

[0264] <Manufacture of black pigment dispersion>

[0265] Mix 200 g of "#960" (manufactured by Mitsubishi Chemical Corporation) as a black pigment, 50 g of DISPERBYK-102 (a polymer dispersant manufactured by BYK Japan KK.) as a pigment dispersant, and 800 g of ion-exchanged water. Use a bead mill (DYNO-MILL KDL A type, manufactured by SHINMARU ENTERPRISES CORPORATION) to disperse zirconia beads with a diameter of 0.5 mm at a filling rate of 60% and a residence time of 2 minutes to obtain a black pigment dispersion (20% by mass of pigment component).

[0266] <Method for measuring charge density>

[0267] The charge density of treatment liquid U-1 in Table 1, the charge density of each white ink in Tables 2 and 3, and the charge density of the water-dispersible resin used in the white inks in Tables 2 and 3 are charge densities based on the streaming potential method and are measured as follows. A colloid particle charge meter ("Model CAS" manufactured by AFG ANALYTIC GmbH) is used for the measurement of charge density.

[0268] (Charge density of treatment liquid and charge density of white ink)

[0269] The white ink and treatment liquid to be measured are each diluted 100 times with ion-exchanged water to prepare test samples, which are titrated with the following titration solutions. The reaction endpoint at which the streaming potential becomes 0 V is measured, and the total charge amount of the diluted treatment liquid and the total charge amount of the diluted white ink are respectively determined based on the usage amount of the titration solution up to the reaction endpoint. The charge density (μeq / g) of the white ink is determined based on the total charge amount of the white ink per unit effective component amount in the diluted white ink. Similarly, the charge density (μeq / g) of the treatment liquid is determined based on the total charge amount of the treatment liquid per unit effective component in the diluted treatment liquid. As the titration solution, for the white ink, a 0.0025N poly(diallyldimethylammonium chloride) (polyDADMAC) solution (manufactured by Fujifilm Wako Pure Chemical Corporation) is used, and for the treatment liquid, a 0.0025N potassium poly(vinyl sulfate) (PVSK) solution (manufactured by Fujifilm Wako Pure Chemical Corporation) is used.

[0270] (Charge density of the water-dispersible resin used in the white ink)

[0271] The aqueous resin emulsion of the water-dispersible resin to be measured is diluted with water so that the solid content becomes 0.05 mass%. Using the resulting diluted solution as a test sample, it is titrated with a 0.0025N poly(diallyldimethylammonium chloride) (polyDADMAC) solution (manufactured by Fujifilm Wako Pure Chemical Corporation). The reaction endpoint at which the streaming potential of the diluted solution becomes 0 V is measured, and the total charge amount of the diluted solution is determined based on the usage amount of the polyDADMAC solution up to the reaction endpoint. The value obtained by dividing the total charge amount of this diluted solution by the solid component amount contained in the diluted solution is the charge density (μeq / g) of the water-dispersible resin.

[0272] <Young's modulus of the dry coating film of the color ink>

[0273] The Young's modulus of the dry coating films of the respective color inks in Tables 4 and 5 is the value obtained as follows. After diluting the color ink with ion-exchanged water so that the total solid content of the pigment and resin in the ink becomes 20% by mass, and flowing the diluted liquid into a PTFE (polytetrafluoroethylene) petri dish so that the dried film thickness becomes 0.4 mm, it is heated and dried at 70 °C for 60 minutes, 120 °C for 20 minutes, and 160 °C for 10 minutes using a thermostatic bath to obtain a dry coating film of the ink. The obtained dry coating film is cut into a dumbbell No. 8 shape specified in JIS K6251 to obtain a test piece. Using a TENSILON universal testing machine (manufactured by A&D Co., Ltd., "RTG-1250"), under the conditions of a tensile speed of 500 mm / minute and a distance between chucks of 20 mm, the stress-strain (elongation rate) curve of the test piece is measured. The stress at an elongation rate of 10% in the obtained stress-strain curve is taken as the Young's modulus [MPa] of the test piece. It should be noted that the film thickness of the dry coating film is obtained based on actual measurement using a micrometer (manufactured by Mitutoyo Corporation, "MDH-25M").

[0274] <Manufacture of Printed Fabrics>

[0275] Tables 6 and 7 show the treatment liquids, white ink, and color inks used in the printed fabrics of Examples 1 to 17 and Comparative Examples 1 to 2.

[0276] In Examples 1 to 17 and Comparative Examples 1 to 2, as the substrate, 100% black cotton T-shirts "Printstar085-cvt" (manufactured by TOMS CO., LTD.) were used.

[0277] In addition, two inkjet printers (TEXTILE PRINTER "MMP-8130" manufactured by Mastermind) were prepared. The treatment liquid was introduced into the first printer (hereinafter, sometimes referred to as "Printer 1"). The white ink and color inks were introduced into the second printer (hereinafter, sometimes referred to as "Printer 2").

[0278] The printed fabrics of Examples 1 to 17 and Comparative Examples 1 to 2 were produced using the following Processes 1 to 4.

[0279] Process 1

[0280] In Process 1, using Printer 1 into which the treatment liquid was introduced, the treatment liquid was applied to the entire area of 100 mm × 200 mm on the substrate so that the application amount of the treatment liquid became 50 g / m 2 ².

[0281] Process 2

[0282] In Step 2, using a printing press 2, white ink is applied to the substrate to which the treatment liquid has been applied by the wet-on-wet method. In this Step 2, on a 100 mm × 200 mm area to which the treatment liquid has been applied, a 100 mm × 200 mm solid white image is printed in such a manner that the application amount of the white ink becomes 200 g / m 2

[0283] Step 3

[0284] In Step 3, using a printing press 2, color ink is applied to the substrate to which the white ink has been applied by the wet-on-wet method. In this step, on a 100 mm × 200 mm area to which the treatment liquid and the white ink have been applied, that is, on a 100 mm × 200 mm solid white image, a 100 mm × 200 mm solid black image is printed in such a manner that the application amount of the color ink becomes 20 g / m 2

[0285]

[0286] Step 4

[0287] In Step 4, for the printed T-shirt, heat treatment is performed at 160 °C for 120 seconds using a Hotronix Fusion heat press (manufactured by Stahls Hotronix).

[0288] <Evaluation>

[0289] The following evaluations are performed. In the evaluation of the "image density of the color ink" and the evaluation of the "cracking of the ink image after washing", the dyed fabric obtained by performing Steps 1 to 4 is used. In the evaluation of the "covering power based on the white ink", the white ink coating film obtained by performing the heat treatment in Step 4 after Step 2 without performing Step 3 is used for evaluation.

[0290] The results are shown in Tables 6 and 7.

[0291] (Covering power based on the white ink)

[0292] The L* value of the solid white image obtained in Step 2 is measured using a spectrophotometer X-Rite eXact, and evaluation is performed according to the following evaluation criteria.

[0293] A: 90 ≤ L*

[0294] B: 85 ≤ L* < 90

[0295] D: L* < 85

[0296] (Image density of the color ink)

[0297] The OD value of the obtained dyed fabric is measured using a spectrophotometer X-Rite eXact, and evaluation is performed according to the following evaluation criteria.

[0297] A: 1.00 ≤ OD

[0298] B: 0.85 ≤ OD < 1.00

[0299] C: 0.75 ≤ OD < 0.85

[0300] D: OD < 0.75

[0301] (Cracking of the ink image after washing)

[0302] Cut the obtained printed fabric into 25 mm × 40 mm to make test pieces. In a 50 mL container, add the test pieces, 10 mm Φ stainless steel balls, and washing water heated to 50°C (0.1 mass% aqueous solution of synthetic detergent for washing), and use a high-speed ball mill stirring mixer swing mill to stir for 10 minutes at a vibration frequency of 60 Hz. After drying the stirred test pieces in an environment at 23°C for 3 hours, visually observe the cracking state of the ink image and evaluate according to the following evaluation criteria.

[0303] A: No cracking is observed

[0304] B: Slight cracking occurs

[0305] D: Cracking is significant [Table 6]

[0306]

[0307] [Table 7]

[0308]

[0309] As shown in each table, Examples 1 to 17 show excellent results in terms of the covering power of white ink, the evaluation of the image density of color ink, and the evaluation of the cracking of the ink image after washing.

Claims

1. A method for manufacturing a printed and dyed article, which comprises: a step of applying a treatment liquid containing a coagulant to a cloth by an inkjet method; a step of applying white ink having a charge density of 30 μeq / g or more to the cloth to which the treatment liquid has been applied by a wet-on-wet method using an inkjet method; and a step of applying colored ink having a Young's modulus of 0.88 MPa or less of a dry coating film to the cloth to which the white ink has been applied by a wet-on-wet method using an inkjet method, wherein the colored ink contains a crosslinking agent, the white ink contains a water-dispersible resin A having a charge density of 55 μeq / g or less and a water-dispersible resin B having a charge density of 75 μeq / g or more.

2. The method for manufacturing a printed and dyed article according to claim 1, wherein the colored ink contains a pigment and a water-dispersible resin, and the mass ratio of the water-dispersible resin to the pigment is 2.5 to 5.0 in terms of water-dispersible resin / pigment.

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