Water-based inkjet ink composition for printing

Abstract

The present invention aims to provide a water-based inkjet ink composition for printing, which can exhibit more excellent image density, higher washing resistance, and appropriate ejection even when printed on cotton and polyester fabrics, and the like. As a solution, a water-based inkjet ink composition for printing is provided, characterized by containing A to E described below: A. Pigment; B1. Solvent having a boiling point of 280°C or higher; B2. As a solvent having a boiling point of 200°C or lower, 0.1 to 6.0% by mass of a glycol ether, and a glycol, relative to the total amount of the water-based inkjet ink composition for printing; here, the mass ratio B1 / B2 of the above-mentioned solvent B1 to the above-mentioned solvent B2 is 0.3 to 3.0; C. Polyurethane resin-based water-dispersible resin; D. Surfactant; E. Blocked isocyanate crosslinking agent, contained at 0.1 to 5.0% by mass, relative to the total amount of the water-based inkjet ink composition for printing.

Description

Technical Field

[0001] This invention relates to water-based inkjet ink compositions for printing and dyeing. Background Technology

[0002] As described in Patent Document 1, a white inkjet ink composition for printing on a pretreated substrate is known, comprising a white pigment, a water-dispersible polyurethane resin that reacts with a cationic compound, a crosslinking agent, a water-soluble organic solvent containing a glycol ether dissolved in 1 to 60 g of water per 100 g, and water. As described in Patent Document 2, it is known to print on fabric using water-based white ink containing two adhesive emulsions.

[0003] As described in Patent Document 3, a specific ink composition is known to be alkaline and the immobilization composition is acidic. When used for printing on a dyed substrate, it can inhibit the movement of the dye and provide excellent wash fastness. As described in Patent Document 4, it is known that excellent washability or abrasion resistance can be achieved by printing on fabric using an ink composition containing a specific polyurethane resin, a surfactant, and a specific organic solvent.

[0004] Patent documents Patent Document 1: Japanese Patent Application Publication No. 2019-35057 Patent Document 2: Japanese Patent Application Publication No. 2017-179263 Patent Document 3: Japanese Patent Publication No. 2020-506264 Patent Document 4: International Publication No. 2020 / 080122 Summary of the Invention

[0005] According to Patent Document 1, although it can have a certain effect as an ink composition for printing and dyeing on cotton fabrics, it is unclear whether it can have an effect on polyester fabrics. According to patent documents 2-4, it is possible to print on fabrics with a certain degree of wash fastness, but it has not been considered that the same effect can be obtained for both cotton and polyester fabrics. Therefore, the objective of this invention is to obtain a water-based inkjet ink composition for printing and dyeing that exhibits superior image density, higher washability, and appropriate ejectibility even when printed on cotton and polyester fabrics.

[0006] The inventors have discovered that the above-mentioned problems can be solved by preparing the following water-based inkjet ink composition for printing and dyeing, thereby completing the following invention. 1. A water-based inkjet ink composition for printing and dyeing, characterized in that it contains the following A to E: A. Pigment; B1. Solvents with a boiling point above 280℃; B2. A glycol ether and a diol, which are solvents with a boiling point below 200°C, comprising 0.1 to 6.0% by mass of the total amount of the water-based inkjet ink composition for printing and dyeing; Here, the mass ratio of solvent B1 to solvent B2, B1 / B2, is 0.3 to 3.0; C. Water-dispersible polyurethane resins; D. Surfactants; E. The water-based inkjet ink composition for printing and dyeing contains 0.1 to 5.0% by mass of a blocked isocyanate crosslinking agent relative to the total amount of the ink. 2. The water-based inkjet ink composition for printing and dyeing according to 1, characterized in that it contains glycerol as solvent B1, a diol containing propylene glycol as solvent B2, and / or dipropylene glycol dimethyl ether as solvent B2. 3. The water-based inkjet ink composition for printing and dyeing according to 1 or 2, characterized in that the polyurethane resin-based water-dispersible resin is a polyester polyurethane resin. 4. An ink group, characterized in that it comprises a pretreatment liquid and an aqueous inkjet ink composition for printing and dyeing, comprising any one of 1 to 3. 5. An inkjet printing method, characterized in that the pretreatment liquid and the water-based inkjet ink composition for printing and dyeing described in any one of 1 to 3 are in contact with each other in a liquid state.

[0007] According to the present invention, a water-based inkjet ink composition for printing and dyeing with suitable ejectibility, sufficient image density, and excellent wash fastness can be obtained. Detailed Implementation

[0008] This invention is based on the following: a water-based inkjet ink composition for printing and dyeing fiber products. The present invention is as follows. In addition, in this specification, "(meth)acrylate" means "acrylate and / or methacrylate", and "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid". In addition, the water-based inkjet ink composition of the present invention is sometimes simply referred to as "ink composition".

[0009] <Ink Composition> [A. Pigment] The ink compositions of this invention can contain pigments of various hues to produce ink compositions of various colors. As this pigment, pigments previously used in ink compositions for printing and dyeing can be used without particular restrictions. Examples of organic pigments include: lake pigments, azo pigments, benzimidazolone pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, perylene pigments, violet ketone pigments, pyrrolopyrrole dione pigments, isoindolinetone pigments, nitro pigments, nitroso pigments, yellow anthrone pigments, quinoline ketone pigments, pinanthrone pigments, and indigo anthraquinone pigments. Examples of inorganic pigments include: carbon black, titanium dioxide, iron oxide red, lead black, iron black, chromium oxide green, and aluminum hydroxide.

[0010] In addition, the following substances can be listed as specific examples of pigments. Examples of yellow pigments include CI pigment yellow 1, 2, 3, 12, 13, 14, 16, 17, 42, 73, 74, 75, 81, 83, 87, 93, 95, 97, 98, 108, 109, 114, 120, 128, 129, 138, 139, 150, 151, 155, 166, 180, 184, 185, and 213, with CI pigment yellow 14, 17, 150, 155, 180, and 213 being preferred examples. Examples of magenta pigments include: CI Pigment Red 5, 7, 12, 22, 38, 48:1, 48:2, 48:4, 49:1, 53:1, 57, 57:1, 63:1, 101, 102, 112, 122, 123, 144, 146, 149, 168, 177, 178, 179, 180, 184, 185, 190, 202, 209, 224, 242, 254, 255, 270, CI Pigment Violet 19, etc., with CI Pigment Red 122, 202, and CI Pigment Violet 19 being preferred examples. Examples of cyan pigments include CI Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 22, 27, 29, 60, etc., with CI Pigment Blue 15:3 and 15:4 being preferred. Examples of black pigments used in black ink compositions include carbon black (CI Pigment Black 7). Examples of white pigments used in white ink compositions include titanium dioxide and aluminum oxide, with titanium dioxide that has been surface-treated with various materials such as aluminum oxide and silicon dioxide being preferred. The pigment content in the ink composition is preferably 1.0 to 20.0% by mass relative to the total mass of the ink composition. If the pigment content is less than 1.0% by mass, the resulting image quality tends to decrease. On the other hand, if it exceeds 20.0% by mass, it tends to have a detrimental effect on the viscosity characteristics of the ink composition. Furthermore, the surface of the pigment particles may or may not be coated with resin. Moreover, the resin used for coating can be either alkali-soluble or alkali-insoluble.

[0011] (Pigment dispersant) The ink composition of the present invention may also contain pigment dispersants as needed. Since pigment dispersants are substances used to improve the dispersibility of pigments and the storage stability of the ink composition of the present invention, conventionally used pigment dispersants can be used without particular limitation, with polymeric dispersants being preferred. Examples of such pigment dispersants include carbodiimide dispersants, polyester amine dispersants, fatty acid amine dispersants, modified polyacrylate dispersants, modified polyurethane dispersants, multi-chain polymeric nonionic dispersants, and polymeric ionic surfactants. These pigment dispersants can be used alone or in combination of two or more. To improve dispersibility, the acid value of the polymeric dispersant is preferably 100 mg KOH / g or higher, more preferably 150 mg KOH / g or higher, and even more preferably 200 mg KOH / g or higher. Among them, acid-modified polyacrylate dispersants are preferred, copolymers of styrene with alkyl acrylate and (meth)acrylic acid are more preferred, and copolymers of styrene with lauryl acrylate and acrylic acid are even more preferred. Regarding the aforementioned pigment dispersant, when the total amount of pigment used is set to 100 parts by mass, it is preferable to contain 1 to 200 parts by mass. If the content of the pigment dispersant is less than 1 part by mass, the dispersibility of the pigment and the storage stability of the ink composition of the present invention may sometimes decrease. On the other hand, it may contain more than 200 parts by mass, but sometimes there is no difference in effect. A more preferred lower limit for the content of the pigment dispersant is 5 parts by mass, and a more preferred upper limit is 60 parts by mass.

[0012] [B1. Solvents with a boiling point above 280°C] Examples of solvents with boiling points above 280°C include glycerol, triethylene glycol, benzyl benzoate, triethanolamine, and triisopropanolamine. Glycerol is preferred among these. The content of a solvent with a boiling point of 280°C or higher in the total amount of the ink composition is preferably 2.0% by mass or more, more preferably 3.0% by mass or more, further preferably 4.0% by mass or more, and most preferably 5.0% by mass or more, provided that it is miscible with the ink composition. Furthermore, it is preferably 20.0% by mass or less, more preferably 17.0% by mass or less, and further preferably 14.0% by mass or less.

[0013] [B2. Specific solvents with a boiling point below 200°C] The present invention uses a glycol ether and a diol in a solvent with a boiling point below 200°C, in an amount of 0.1 to 6.0% by mass relative to the total amount of the water-based inkjet ink composition for printing and dyeing. Examples of glycol ethers include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol tert-butyl ether, ethylene glycol isobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, and (mono- or di)alkyl ethers of the diols of 3-methoxy-3-methyl-1-butanol. Other examples include: (mono- or di) alkyl ethers of dialkylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and dipropylene glycol mono-n-butyl ether. Examples of diols include ethylene glycol, propylene glycol, and 1,2-butanediol.

[0014] The content of glycol ethers and diols with boiling points below 200°C in the total amount of the ink composition is preferably 8.0% by mass or more, more preferably 10.0% by mass or more, and even more preferably 11.0% by mass or more, provided that each solvent is miscible with the ink composition. Furthermore, it is preferably 20.0% by mass or less, more preferably 18.0% by mass or less, and even more preferably 16.0% by mass or less. The content of glycol ethers with a boiling point below 200°C in the total amount of the ink composition is 0.1 to 6.0% by mass. Preferably, it is 0.5% by mass or more, more preferably 0.8% by mass or more, further preferably 1.5% by mass or more, and most preferably 2.0% by mass or more. Furthermore, it is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and further preferably 3.5% by mass or less. If the glycol ethers with a boiling point below 200°C are not present, or if the content is less than 0.1% by mass, the wash fastness will deteriorate. Furthermore, if it exceeds 6.0% by mass, the spraying stability will worsen. Furthermore, the content of diols with a boiling point below 200°C in the total amount of the ink composition is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, even more preferably 5.0% by mass or more, and most preferably 7.0% by mass or more. It is also preferably 20.0% by mass or less, more preferably 17.0% by mass or less, even more preferably 14.0% by mass or less, and most preferably 11.0% by mass or less. By containing diol ethers and diols with a boiling point below 200°C, wash fastness can be improved.

[0015] Furthermore, the mass ratio of solvent B1 to solvent B2, B1 / B2, is 0.3 to 3.0, preferably 0.4 or more, more preferably 0.5 or more, and even more preferably 0.6 or more. It is also preferably 2.5 or less, more preferably 1.8 or less, and even more preferably 1.3 or less. If this mass ratio B1 / B2 is less than 0.3, the inkjet ink composition will have poor ejectibility; conversely, if it is greater than 3.0, the wash fastness will decrease.

[0016] (Other solvents) In this invention, other solvents may be included or may not be included, without compromising the effects of the invention. Examples of glycol ethers and diols with boiling points exceeding 200°C and below 280°C include: ethylene glycol monophenyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dipropylene glycol mono-n-propyl ether. Other examples include: diethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,6-hexanediol, neopentanediol, 1,2-cyclohexanediol, heptahydrin, 1,8-octanediol, etc.

[0017] Solvents other than glycol ethers and diols with boiling points below 280°C can be selected from monohydric alcohols, alkyl ether acetates of glycols, ketones, ethers, esters, nitrogen-containing compounds, etc. These can be used alone or in combination of two or more. Examples of monohydric alcohols mentioned above include: methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol or their isomers, cyclopentanol, cyclohexanol, benzyl alcohol, etc. Examples of alkyl ether acetates that are glycols include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate.

[0018] Examples of ketones include: acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and diacetone alcohol. Examples of ethers include 1,3-dioxane, 1,4-dioxane, diethyl ether, tetrahydrofuran, and diethylene glycol butyl methyl ether. Examples of esters include: methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, n-propyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, tripropylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, etc. Examples of nitrogen-containing compounds include: monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine, N-methylethanolamine, N-methyldiethanolamine, N-methyl-2-pyrrolidone, N,N-dimethylformamide, etc.

[0019] [C. Water-dispersible polyurethane resins] Examples of water-dispersible polyurethane resins that can be used in this invention include polyester polyurethane resins, polyether polyurethane resins, polyether ester polyurethane resins, and polycarbonate polyurethane resins. Polyester polyurethane resins are preferred. The polyurethane resin used herein is preferably an anionic polyurethane resin, which is a reaction product of a polyisocyanate compound and one or more polyol compounds and polyamine compounds selected from polyesters, polylactones, polycarbonates and polyethers / polycarbonates, with anionic polyester polyurethane resins being preferred. Furthermore, in the application of the present invention, the 100% modulus (determined based on DIN53504 (test for rubber elastomers)) is preferably 0.5 to 10.0 MPa. Furthermore, specific examples of polyester polyurethane resins include: "Superflex210" (anionic polyester polyurethane resin), "Superflex300" (anionic polyester polyurethane resin), "Superflex500M" (nonionic polyester polyurethane resin) (all from Daiichi Kogyo Pharmaceutical Co., Ltd.), "Impranil DLP1380" (anionic polyester polyurethane resin), "Impranil DLN-W50" (polyurethane resin), "Impranil DLU" (polyurethane resin), "Impranil DLP-R" (a polyester polyurethane resin containing sulfonic acid groups), and "Baybond PU407" (anionic polyester polyurethane resin) (all from Sumika Covestro Urethane Co., Ltd.).

[0020] (Other resins) Without impairing the effects of the present invention, the water-based inkjet ink composition for printing and dyeing of the present invention may contain other resins that are not water-dispersible resins of the polyurethane resin class mentioned above. For example, when preparing a resin varnish containing the above-mentioned pigment in order to obtain an ink composition, an alkali-soluble resin that is soluble in an alkaline aqueous solvent can be used. As such an alkali-soluble resin, it is preferable to have one or more anionic groups such as carboxyl groups, sulfonic acid groups, and phosphonic acid groups (-P(=O)(OH2)). Furthermore, the aforementioned alkali-soluble resin, as the hydrophobic portion mainly used to improve the adsorption of pigments, preferably has hydrophobic groups such as long-chain alkyl, alicyclic, or aromatic cyclic hydrocarbon groups. By adjusting the alkali-soluble resin, the ink composition in the printing area can be prevented from seeping out.

[0021] From the perspective of improving solubility in aqueous media, the acid value of the aforementioned alkali-soluble resin is preferably 100 mg KOH / g or higher, more preferably 140 mg KOH / g or higher. Furthermore, from the perspective of improving the water resistance of printed materials, the acid value of the aforementioned alkali-soluble resin is preferably 300 mg KOH / g or lower, more preferably 250 mg KOH / g or lower. Additionally, the aforementioned acid value is a theoretical acid value obtained by arithmetically calculating the number of mg of potassium hydroxide theoretically required to neutralize 1 g of alkali-soluble resin based on the monomer composition used in the synthesis of the alkali-soluble resin.

[0022] From the perspective of improving the storage stability and ejection stability of the ink composition, the glass transition temperature of the aforementioned alkali-soluble resin is preferably 0°C or higher, more preferably 10°C or higher. From the perspective of improving the tactile feel of the printed matter, the glass transition temperature of the aforementioned alkali-soluble resin is preferably 100°C or lower, more preferably 80°C or lower. The glass transition temperature of the aforementioned alkali-soluble resin, when the alkali-soluble resin is an acrylic copolymer resin, is the theoretical glass transition temperature obtained by the following Wood formula. Wood formula: 1 / Tg=W1 / Tg1+W2 / Tg2+W3 / Tg3+·····+Wx / Tgx [In the formula, Tg1~Tgx represent the glass transition temperatures of the homopolymers of monomers 1, 2, 3...x constituting the alkali-soluble resin, W1~Wx represent the polymerization fractions of monomers 1, 2, 3...x, and Tg represents the theoretical glass transition temperature. The glass transition temperature in Wood's formula is an absolute temperature.]

[0023] When the alkali-soluble resin is not an acrylic copolymer resin, the glass transition temperature of the aforementioned alkali-soluble resin is a measured glass transition temperature obtained by thermal analysis. As a method for thermal analysis, the glass transition temperature can be determined according to Japanese Industrial Standard JIS K7121 (Method for Determination of Transition Temperature of Plastics). For example, a PerkinElmer Pyris1 DSC can be used to measure the glass transition temperature under conditions of a heating rate of 20°C / min and a nitrogen flow rate of 20 mL / min.

[0024] From the perspective of improving the water resistance of printed materials, the weight-average molecular weight of the aforementioned alkali-soluble resin is preferably 5,000 or more, and more preferably 10,000 or more. From the perspective of improving the solubility of the aforementioned alkali-soluble resin in aqueous media, the weight-average molecular weight is preferably 100,000 or less, and more preferably 50,000 or less. The aforementioned weight-average molecular weight can be determined by gel permeation chromatography (GPC). As an example, a Water 2690 (Waters Corporation) was used as the GPC apparatus, a PLgel, 5 μm, MIXED-D (Polymer Laboratories Corporation) column was used as the chromatographic column, tetrahydrofuran was used as the developing solvent, and chromatographic analysis was performed under the conditions of column temperature 25°C, flow rate 1 mL / min, RI detector, sample injection concentration 10 mg / mL, and injection volume 100 μL. The weight-average molecular weight was then converted to that of polystyrene.

[0025] Examples of alkali-soluble resins include acrylic copolymer resins, maleic acid copolymer resins, polyester resins obtained by polycondensation reactions, and polyurethane resins. Regarding materials used in the synthesis of such alkali-soluble resins, as disclosed in Japanese Patent Application Publication No. 2000-94825, acrylic copolymer resins, maleic acid copolymer resins, polyester resins, and polyurethane resins obtained using the materials described in that publication can be used. Furthermore, resins obtained from materials other than those used can also be used. Two or more of the aforementioned alkali-soluble resins can be used alone or in combination. Additionally, alkali-soluble resins that serve as pigment dispersants can also be used. When the water-based inkjet ink composition for printing and dyeing of the present invention contains an alkali-soluble resin, the content of the alkali-soluble resin, relative to the total water-based inkjet ink composition for printing and dyeing of the present invention, is preferably 0.2% by mass or more, more preferably 0.4% by mass or more, based on the solid component of the alkali-soluble resin. Especially in the case of colored inks that are not white, by containing 0.4% by mass or more of the alkali-soluble resin, bleeding of the printed and dyed materials can be further prevented.

[0026] As the aforementioned acrylic copolymer resin, for example, a mixture of other monomers that can copolymerize with monomers containing anionic groups can be used, and the mixture is polymerized in a solvent in the presence of a common free radical generator (e.g., benzoyl peroxide, tert-butyl peroxide, azobisisobutyronitrile, etc.).

[0027] As for the aforementioned monomers containing anionic groups, examples include monomers having at least one anionic group selected from carboxyl, sulfonic acid, and phosphonic acid groups, among which monomers having carboxyl groups are particularly preferred. Examples of monomers containing a carboxyl group include: acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, maleic anhydride, fumaric anhydride, and maleic half-ester. Examples of monomers containing a sulfonic acid group include ethanesulfonate methacrylate. Examples of monomers containing a phosphonic acid group include ethyl phosphate methacrylate.

[0028] From the perspective of improving pigment adsorption, monomers containing hydrophobic groups are preferred as other monomers that can copolymerize with the aforementioned monomers containing anionic groups. Examples of monomers containing a hydrophobic group, for instance, those having long-chain alkyl groups, include: alkyl esters of free radical polymerizable unsaturated carboxylic acids such as (meth)acrylic acid with 8 or more carbon atoms (e.g., 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxystearyl (meth)acrylate, etc.); alkyl vinyl ethers with 8 or more carbon atoms (e.g., dodecyl vinyl ether, etc.); and vinyl esters of fatty acids with 8 or more carbon atoms (e.g., vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate, etc.); monomers having alicyclic hydrocarbon groups, such as cyclohexyl (meth)acrylate; and monomers having aromatic hydrocarbon groups, such as benzyl (meth)acrylate, styrene, α-methylstyrene, vinyltoluene, and other styrene monomers. The aforementioned monomers containing hydrophobic groups can be used alone or in combination of two or more.

[0029] Other monomers that can be copolymerized with the aforementioned monomers containing anionic groups may include monomers containing hydrophilic groups, from the perspective of inhibiting the aggregation of alkali-soluble resins in aqueous media. Examples of monomers containing hydrophilic groups include, for instance, monomers having (poly)alkylene oxide chains such as: esterifications of mono-terminated alkyl-capped (poly)alkylene glycols with free radical polymerizable unsaturated carboxylic acids such as (meth)acrylic acid, or ethylene oxide adducts and / or propylene oxide adducts of free radical polymerizable unsaturated carboxylic acids such as (meth)acrylic acid; examples of monomers containing basic groups include: vinylpyrrolidones such as 1-vinyl-2-pyrrolidone and 1-vinyl-3-pyrrolidone, vinylpyridines such as 2-vinylpyridine, 4-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, and 1-vinyl... Imidazole, 1-vinyl-2-methylimidazolium and other vinylimidazolium derivatives; 3-vinylpiperidine, N-methyl-3-vinylpiperidine and other vinylpiperidine derivatives; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate; methacrylamide, N-hydroxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-methoxy (meth)acrylamide, N-ethoxy (meth)acrylamide, N-dimethylacrylamide, N-propylacrylamide and other nitrogen-containing derivatives of (meth)acrylic acid; hydroxyl groups, for example, hydroxyethyl methacrylate, hydroxypropyl methacrylate and other hydroxyalkyl esters of (meth)acrylic acid; epoxy groups, for example, glycidyl methacrylate and other epoxy groups. The aforementioned monomers containing hydrophilic groups can be used alone or in combination of two or more.

[0030] Other copolymerizable monomers besides the aforementioned monomers containing hydrophobic and hydrophilic groups include, for example, alkyl esters of (meth)acrylic acid with fewer than 8 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, and hexyl (meth)acrylate. These other copolymerizable monomers besides the aforementioned monomers containing hydrophobic and hydrophilic groups can be used alone or in combination of two or more.

[0031] Regarding the aforementioned alkali-soluble resin, from the perspective of moderately crosslinking with the resin and inhibiting pigment aggregation, crosslinking agents with two or more functions can also be used. In order to react with the functional groups of alkali-soluble resins, the aforementioned crosslinking agent with two or more functional groups can be a crosslinking agent having two or more reactive functional groups within its molecule. Examples of such reactive functional groups include epoxy, hydroxyl, isocyanate, amino, and aziridinyl groups. The aforementioned crosslinking agents with two or more functional groups can be used alone or in combination.

[0032] [D. Surfactants] The preferred surfactants are nonionic surfactants and / or amphoteric surfactants. As a nonionic surfactant, one or more of the following can be selected: organosilicon surfactants, fluorinated surfactants, and acetylene surfactants. Examples of organosilicon surfactants include SILFACE SAG001, SILFACE SAG002, SILFACE SAG003, SILFACE SAG005, and SILFACE SAG503A (all from Nissin Chemical Industries Co., Ltd.), with polyether-modified silicones being preferred. Further examples include polyether-modified polydimethylsiloxanes such as BYK-300, BYK-302, BYK-306, BYK-307, BYK-330, BYK-333, BYK-347, BYK-377, and BYK-3455, and even more specifically, BYK-3456 (and above, BYK Chemical Japan).

[0033] Examples of fluorinated surfactants include F-410, F-444, F-553 (and above, manufactured by DIC), FS-65, FS-34, FS-35, FS-31, and FS-30 (and above, manufactured by DuPont).

[0034] Examples of acetylene surfactants include Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol 104BC, Surfynol 104DPM, Surfynol 104PA, Surfynol 104PG-50, Surfynol 420, Surfynol 440, Surfynol 465 (and above, EVONIK), Dynol 607, Dynol 609, Olfine E1004, Olfine E1010, Olfine E1020, Olfine PD-001, Olfine PD-002W, Olfine PD-004, Olfine PD-005, Olfine EXP.4001, Olfine EXP.4200, and Olfine... One or more commercially available products under trade names such as EXP.4123 and Olfine EXP.4300 (or higher, Nissin Chemical Industries, Ltd.). Among them, acetylene glycol ethers formed by the addition of polyoxyethylene are preferred.

[0035] Examples of amphoteric surfactants include: alkyl betaine surfactants such as lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyl dimethylaminoacetic acid betaine; and alkyl amine oxide surfactants such as lauryl dimethylamine oxide. Further specific examples include: AMPHITOL 20AB, AMPHITOL 20BS, AMPHITOL 24B, AMPHITOL 55AB, AMPHITOL 86B, AMPHITOL 20Y-B, ​​AMPHITOL 20N (all from Kao Corporation), etc.

[0036] These surfactants preferably include acetylene surfactants, organosilicon surfactants, and amphoteric surfactants. The total content of surfactants in the ink composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more. Furthermore, it is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.6% by mass or less.

[0037] [E. Crosslinking agent] The ink composition of the present invention contains a crosslinking agent, which improves wash fastness. Specifically, in terms of excellent curability and wash fastness, it contains 0.1 to 5.0% by mass of a blocked isocyanate crosslinking agent relative to the total amount of the water-based inkjet ink composition for printing and dyeing. Blocked isocyanate crosslinking agents are substances obtained by pre-reacting and passivating the active isocyanate groups in polyisocyanate compounds with blocking agents such as phenol. Blocked isocyanates cannot undergo crosslinking reactions in this state and are chemically stable. However, when the protecting groups bonded to the isocyanate groups are dissociated due to heat treatment or other methods to form active isocyanate groups, they become capable of crosslinking reactions.

[0038] The compounds constituting the polyisocyanate portion of the blocked isocyanate crosslinking agent are preferably diisocyanate compounds, triisocyanate compounds, or polyisocyanate compounds, such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene triisocyanate, lysine ester triisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, etc. Among these, triisocyanate compounds, such as hexamethylene diisocyanate modified forms of triuret, are more preferred.

[0039] Compounds constituting this polyisocyanate moiety can be categorized as polyisocyanate compounds having two or more isocyanate groups per molecule, such as diisocyanate compounds, triisocyanate compounds, tetraisocyanate compounds, pentaisocyanate compounds, hexaisocyanate compounds, and various other polyisocyanate compounds. Specific examples of polyisocyanate compounds include: aromatic polyisocyanates such as toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, methylene bis(phenyl isocyanate), and isophorone diisocyanate; alicyclic polyisocyanates such as hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; and aliphatic polyisocyanates such as 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. The polyisocyanate compound constituting the blocked isocyanate in this invention can be one or more. From the perspective of more smoothly curing the ink composition, the polyisocyanate compound constituting the blocked isocyanate in this invention preferably contains a triisocyanate compound.

[0040] The blocking agent for the blocked isocyanate crosslinking agent is not particularly limited. In addition to phenol mentioned above, cresol, ethylphenol, butylphenol, 2-hydroxypyridine, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, butanethiol, dodecyl mercaptan, acetanilide, acetamide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, succinimide, maleimide, imidazole, 2-methylimidazole, urea, thiourea, ethylene urea, formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, carbazole, dimethylpyrazole, triazole, etc., can be used. The blocking agent constituting the blocked isocyanate compound of this invention can be one or more. Furthermore, the combination of the blocking agent and the polyisocyanate compound is not particularly limited, and there can be multiple combinations. The blocked isocyanate crosslinking agent of this invention can be composed of multiple compounds.

[0041] The blocked isocyanate crosslinking agent is preferably thermally decomposable. In the case of a thermally decomposable type, the temperature at which the dissociation reaction of the blocking agent becomes significant (hereinafter referred to as the "unblocking temperature") can be adjusted according to the type of blocking agent or the type of polyisocyanate compound being blocked. There is no particular limitation on the specific unblocking temperature; for example, at 70–130°C, the water-based inkjet ink composition containing a blocked isocyanate compound with this unblocking temperature has a low or essentially zero crosslinking density before crosslinking. However, by forming a crosslinked structure through a crosslinking reaction, the crosslinking density can be increased.

[0042] The crosslinking agent content is 0.1 to 5.0% by mass relative to the total amount of the ink composition of the present invention. Preferably, it is 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more. Furthermore, it is preferably 4.5% by mass or less, more preferably 4.0% by mass or less, and even more preferably 3.5% by mass or less. If it is less than 0.1% by mass, the wash fastness may decrease; if it exceeds 5.0% by mass, the sprayability may decrease.

[0043] (Other crosslinking agents) Other crosslinking agents may be used in combination without impairing the effects of the present invention. For example, a water-soluble acrylic resin containing an oxazoline group may be used as such a crosslinking agent.

[0044] (Other ingredients) The water-based inkjet ink composition for printing and dyeing of the present invention may contain various additives such as ultraviolet absorbers, antioxidants, defoamers, freshness improvers, mildew inhibitors, rust inhibitors, thickeners, humectants, and pH adjusters as other components.

[0045] (UV absorber) Ultraviolet absorbers include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylates, hydroxyphenyltriazine-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, nickel complex-based ultraviolet absorbers, etc.

[0046] (Antioxidants) Antioxidants include phenolic antioxidants, amine antioxidants, sulfur antioxidants, phosphorus antioxidants, etc.

[0047] (Defoamer) Defoamers include silicone-based defoamers, Pluronic (registered trademark), and other similar products.

[0048] (Preparation method of ink composition) <Preparation Method of Ink Composition> There are no particular limitations on the method for preparing (manufacturing) ink compositions. The above-mentioned components can be added sequentially or simultaneously and mixed. For example, the following methods can be listed: (1) A method for preparing an ink composition by mixing an aqueous resin varnish obtained by dissolving an alkali-soluble resin in water in the presence of an alkaline compound, a pigment, a pigment dispersant as needed, etc., and then preparing a pigment dispersion (ink base) using various dispersers, such as ball mills, vertical ball mills (attritors), roller mills, sand mills, agitator mills, etc., and then further adding the remaining materials; or (2) A method for preparing an ink composition by dispersing the pigment by the above method, obtaining a resin-coated pigment by precipitating the alkali-soluble resin to the pigment surface by acid precipitation or ion exchange method as described in Publication No. WO2005 / 116147, then neutralizing the obtained resin-coated pigment with an alkaline compound, and then dispersing it again in water using various dispersers (high-speed stirring devices, etc.), and then further adding the remaining materials. The initial viscosity of the aforementioned ink composition after manufacturing is 2.0 to 25.0 mPa·s, preferably in the range of 5.0 to 20.0 mPa·s. The viscosity can be measured, for example, using an E-type viscometer (trade name "RE100L type viscometer", manufactured by Toki Sangyo Co., Ltd.).

[0049] <Pretreatment solution> The pretreatment liquid in this invention is a substance used to form a pretreatment layer on the printed object before the printing layer is formed, so that the printing layer composed of the water-based inkjet ink composition of this invention can firmly adhere to the printed object. The pretreatment solution is basically an aqueous solution containing acidic components and / or their salts, as well as alkaline substances as pH adjusters.

[0050] (acid) As acids, organic acids, inorganic acids, and their alkali metal salts or alkaline earth metal salts can be used. Depending on the context, these acids and their salts may sometimes be collectively referred to as "acid compounds." As organic acids, carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, citric acid, and lactic acid are preferred, with formic acid and acetic acid, which have a boiling point of 120°C or less at 1 atmosphere, being more preferred. Formic acid (boiling point 100.8°C at 1 atmosphere) and / or acetic acid (boiling point 118°C at 1 atmosphere) can be used as organic acids with a boiling point of 120°C or less. Furthermore, sodium, potassium, magnesium, calcium, or ammonium salts of formic acid or acetic acid can also be used. The content of this acid compound in the pretreatment solution is preferably 2.0% by mass or more, more preferably 3.0% by mass or more, and even more preferably 3.5% by mass or more. Furthermore, it is preferably 10.0% by mass or less, more preferably 8.0% by mass or less, and even more preferably 7.0% by mass or less. If the content of acidic compounds is too low, the color development of the ink composition printed on it may be insufficient. Conversely, if the content is excessive, the acidity may become too strong, or the free organic acid may require time to evaporate after printing until it disappears from the print or image. Furthermore, especially when the boiling point of the organic acid is below 120°C, it is expected to shorten the time required for the free organic acid to evaporate after printing until it disappears from the print or image.

[0051] (surfactant) The pretreatment solution may or may not contain a surfactant. As a possible surfactant, a nonionic surfactant is preferred. Among these, acetylene surfactants are preferred. The surfactant content is, for example, 0 to 1.0% by mass relative to the total pretreatment solution, preferably 0.01 to 1.0% by mass, more preferably 0.1 to 0.7% by mass.

[0052] The nonionic surfactant is selected from silicone surfactants, fluorinated surfactants, and acetylene surfactants. Furthermore, these surfactants can be used alone in the ink composition described above.

[0053] (solvent) The pretreatment solution in this invention may use only water, or a mixture of water and a water-soluble organic solvent, as the solvent. Examples of water-soluble organic solvents that can be used in the ink compositions described above include monohydric alcohols, trihydric alcohols, dihydric alcohols, polyhydric alcohols of four or more members, lower alkyl ethers of polyhydric alcohols, ketones, ethers, esters, and nitrogen-containing compounds. These can be used alone or in combination of two or more. Furthermore, they can be the same as or different from the water-soluble organic solvent used in the ink compositions described above. The content of the aforementioned water-soluble organic solvents should preferably be minimized, or it may be optional to omit them. The solvent content in the pretreatment solution is preferably 0 to 10.0% by mass, more preferably 0 to 5.0% by mass. When it exceeds 10.0% by mass, poor drying or reduced anti-blocking properties may occur.

[0054] (pH adjuster) The pretreatment solution in this invention may or may not contain a pH adjuster. As a pH adjuster, it can be an alkaline, water-soluble polyvalent metal salt, such as ammonia, methylamine, ethylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, triethanolamine, etc. Among them, organic alkaline substances are preferred, and ammonia is even more preferred. The content of the pH adjuster in the pretreatment solution is preferably 0-10.0% by mass, more preferably 0-5.0% by mass, even more preferably 0-3.0% by mass, and most preferably 0-1.0% by mass.

[0055] The alkaline, water-soluble polyvalent metal salt used as the pH adjuster is a salt of an organic or inorganic polyvalent metal that has a solubility of 1 g / 100 mL or more in 100 mL of water at 20°C, preferably 2 g / 100 mL or more, and more preferably 20 g / 100 mL or more (wherein the organic acid is a substance with a boiling point exceeding 120°C). Water-soluble polyvalent metal salts can be either complex salts containing polyvalent metals or hydrates. As a multivalent metal, it can be one or more selected from magnesium, calcium, strontium, zinc, copper, iron and aluminum.

[0056] Organic acids that constitute water-soluble polyvalent metal salts include, for example, one or more fatty acids represented by RCOOH (where R is an organic group with 1 to 30 carbon atoms). Examples of such organic acids include: acetic acid, propionic acid, octanoic acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, 12-hydroxystearic acid, ricinoleic acid, oleic acid, isoleic acid, linoleic acid, linolenic acid, arachidic acid, benzyl acid, ceramide, ceramide, linoleic acid, linolenic acid, beeswax acid, lactic acid, citric acid, gluconic acid, malic acid, tartaric acid, succinic acid, malonic acid, glutaric acid, maleic acid, fumaric acid, penteneric acid, benzoic acid, ascorbic acid, etc. As inorganic acids, examples include one or more selected from nitric acid, sulfuric acid, hydrogen chloride (hydrochloric acid), hydrogen bromide, hydrogen iodide, chloric acid, bromic acid, carbonic acid, phosphoric acid, etc.

[0057] Water-soluble polyvalent metal salts belonging to the category of organic acids may be selected from one or more of the following: zinc acetate, calcium acetate, strontium acetate, magnesium acetate, zinc formate, calcium formate, strontium formate, copper formate (II), magnesium formate, calcium benzoate, magnesium benzoate, zinc benzoate, calcium lactate, magnesium lactate, aluminum lactate, ferric lactate (II), copper lactate, calcium ascorbate, magnesium ascorbate, calcium propionate, magnesium propionate, calcium gluconate, magnesium gluconate, zinc gluconate, copper gluconate, zinc citrate, copper citrate, and their hydrates.

[0058] In addition, water-soluble polyvalent metal salts belonging to inorganic acids may be selected from one or more of the following: zinc chloride, aluminum chloride, calcium chloride, strontium chloride, ferric chloride, copper(II) chloride, nickel chloride, magnesium chloride, manganese(II) chloride, zinc bromide, calcium bromide, strontium bromide, ferric bromide(II), copper(II) bromide, magnesium bromide, zinc iodide, calcium iodide, magnesium iodide, aluminum nitrate, calcium nitrate, strontium nitrate, ferric nitrate(III), copper(II) nitrate, magnesium nitrate, zinc sulfate, aluminum sulfate, ferric sulfate(II), ferric sulfate(III), copper sulfate, magnesium sulfate, potassium aluminum sulfate, calcium dihydrogen phosphate, calcium bicarbonate, and their hydrates.

[0059] (Other ingredients) Furthermore, it can contain surfactants, preservatives, ultraviolet absorbers, antioxidants, defoamers, freshness improvers, mildew inhibitors, rust inhibitors, thickeners, humectants, etc., similar to water-based inkjet ink compositions for printing and dyeing.

[0060] (Pretreatment solution preparation method) There are no particular limitations on the method for preparing the pretreatment solution of this invention. The above-mentioned components can be added sequentially or simultaneously, and then mixed and stirred.

[0061] [Ink Set] The ink kit of the present invention is composed of any combination of the pretreatment liquid and the ink composition described above. There are no particular limitations on the combination of the pretreatment liquid and the ink composition in the ink kit, and the type or amount of color of the ink composition can be arbitrarily determined.

[0062] [Printed material] The printed matter treated with the ink composition of the present invention includes various types of paper and fiber products that are known to be printable and dyeable with the ink composition for printing and dyeing. Examples of fiber products include cloth, fabric, and clothing. There are no particular restrictions on the types of fibers used in fiber products. Examples of fibers that can be selected from polyester, cellulose, acrylic resins such as polymethyl methacrylate, polyamide resins such as nylon, and natural fibers or their blends are also acceptable. Polyester fibers include those with polyethylene terephthalate as the main component. Cellulose fibers include cotton, kapok, hemp, rayon, triacetate, and diacetate. Polyamide fibers include nylon. In addition, natural fibers include silk and wool.

[0063] Printing method based on the water-based inkjet ink composition of the present invention The printing method based on the water-based inkjet ink composition for printing and dyeing according to the present invention includes a method of inkjet printing in which a pretreatment liquid and an ink composition are brought into contact with each other in a liquid state. This contact in a liquid state refers to a method of printing using a wet-on-wet mode, where the pretreatment liquid is applied to the surface of the workpiece and, while the pretreatment liquid on the coated surface is still wet (i.e., while it remains in a liquid state), the inkjet printing apparatus is used to print using the water-based inkjet ink composition for printing and dyeing. Furthermore, the printing of the image onto the substrate can be performed by providing the ink composition of the present invention to a low-viscosity printhead of an inkjet printer, and then ejecting the ink composition from the printhead with a coating thickness of, for example, 1 to 60 μm relative to the substrate. Conventional inkjet printing apparatuses can be used as the printing device for printing the ink composition of the present invention.

[0064] Specifically, one method for printing and curing the water-based inkjet ink composition of the present invention can be described as a method of heating and curing a coating of the ink composition of the present invention applied to the surface of the printed object. As an apparatus for heat curing, a known apparatus for curing heat-curing ink compositions can be used. Examples of heat sources include devices that directly contact the substrate for heating, such as infrared rays, heating wires, or irons, or devices that use radiation from infrared lamps or heating wires without contacting the substrate. Example

[0065] The following examples illustrate the invention in more detail, but the invention is not limited to these examples. Furthermore, unless otherwise stated, "%" refers to "mass %" and "parts" refers to "parts by mass". Additionally, the numerical values ​​for the quantities of each material in the table are also "parts by mass". Table 1 below shows examples of the formulation of water-based inkjet ink compositions for printing and dyeing, and Table 2 shows the evaluation results of the examples and comparative examples.

[0066] [Preparation of Pretreatment Solution] (Pretreatment solution A) Add 5.0 parts formic acid and 0.2 parts Surfynol 440 (acetylene glycol surfactant, HLB=8, EVONIK) to 94.8 parts of water and stir to obtain pretreatment solution A. (Pretreatment solution B) Add 5.0 parts of calcium formate and 0.2 parts of Surfynol 440 (acetylene glycol surfactant, HLB=8, EVONIK) to 94.8 parts of water and stir to obtain pretreatment solution B.

[0067] [Preparation of Ink Compositions] (Water-based acrylic resin varnish) 25 parts of an acrylic / lauryl acrylate / styrene copolymer with a weight average molecular weight of 30,000 and an acid value of 220 mg KOH / g were dissolved in a mixed solution of 3.5 parts potassium hydroxide and 71.5 parts water to obtain an aqueous acrylic resin varnish with a solid content of 25% as an alkali-soluble resin solution.

[0068] (pigment) Titanium oxide (trade name "Tipaque CR-90", alumina / silica treated, average single-pass particle size 0.25μm, oil absorption 21ml / 100g, Ishihara Sangyo Co., Ltd.) Blue pigment (CI Pigment Blue 15:3) Yellow pigment (CI Pigment Yellow 14) Red pigment (CI Pigment Red 122) Black pigment (CI Pigment Black 7)

[0069] (Preparation of water-based white ink base) Add 19 parts of water to 36 parts of the above-mentioned water-based acrylic resin varnish and mix. Then add 45 parts of titanium oxide and stir to mix. Finally, knead the mixture through a wet circulating mill to obtain a water-based white ink base. (Preparation of water-based blue ink base) Add 64 parts of water to 16 parts of the above-mentioned water-based acrylic resin varnish and mix. Then add 20 parts of blue pigment and stir to mix. Finally, knead the mixture through a wet circulating mill to obtain a water-based blue ink base. (Preparation of water-based yellow ink base) Add 64 parts of water to 16 parts of the above-mentioned water-based acrylic resin varnish and mix. Then add 20 parts of yellow pigment and stir to mix. Finally, knead the mixture through a wet circulating mill to obtain a water-based yellow ink base. (Preparation of water-based red ink base) Add 64 parts of water to 16 parts of the above-mentioned water-based acrylic resin varnish and mix. Then add 20 parts of red pigment and stir to mix. Finally, knead the mixture through a wet circulating mill to obtain a water-based red ink base. (Preparation of water-based black ink base) Add 64 parts of water to 16 parts of the above-mentioned water-based acrylic resin varnish and mix. Then add 20 parts of black pigment and stir to mix. Finally, knead the mixture through a wet circulating mill to obtain a water-based black ink base.

[0070] (Ink composition) The composition of the ink composition used in Table 1 below is shown below. Water-based acrylic resin varnish (the same varnish used in the preparation of the base materials for the above-mentioned colored inks (25% solids)) Impranil DLP-R: Sulfonic acid modified polyester polyurethane resin emulsion, 50% solids content, 100% modulus 0.9 MPa, Sumika Covestro Urethane Co. Impranil DLN-W50: Anionic polyester polyurethane resin emulsion, 50% solids content, 100% modulus 1.7 MPa, Sumika Covestro Urethane Co. Impranil DLU: Anionic polyether / polycarbonate polyurethane resin emulsion, 60% solids content, 2.0 MPa modulus per 100% of its product, manufactured by Sumika Covestro Urethane. Mowinyl 966A: Styrene-acrylic resin emulsion, 45% solids, Japan CoatingResin Co., Ltd. Bayhydur BL2867: A hydroxyl-containing blocked isocyanate crosslinking agent, 38% solids content, Covestro. EPOCROS WS-700: A carboxyl-containing oxazoline crosslinking agent, 25% solids content, manufactured by Nippon Shokubai Co., Ltd. CARBODILITE V-02: Polycarbodiimide resin, 40% solids content, Nisshinbo Chemical Co., Ltd. E1010: Olfine-E1010: Polyoxyethylene (10) Gynethinyl Ether, Nissin Chemical Co., Ltd.

[0071] (Printing with white ink composition) On a black fabric made of 100% polyester and 100% cotton, to achieve 800g / m² 2 Pretreatment solution A or B was applied in a manner to obtain a printing medium. Using an evaluation printer equipped with a printhead manufactured by SPECTRA and inkjet printing ink compositions 1-12 and 17-25, a solid image was printed on the aforementioned printing medium. The medium was then heated in a conveyor oven at 110°C for 12 minutes to obtain printed products of Examples 1-13 and Comparative Examples 1-9, each made from a white ink composition.

[0072] (Printing of colored ink compositions) On a black fabric made of 100% polyester and 100% cotton, to achieve 800g / m² 2Pretreatment solution A or B is applied in a manner to obtain a printing medium. Using an evaluation printer equipped with a printhead manufactured by SPECTRA and ink composition 1 (white ink composition for inkjet printing), a solid image is printed on the aforementioned printing medium. Solid images of ink compositions 13 to 16 (color ink compositions for inkjet printing) are then printed on the solid image. The medium is then heated in a conveyor oven at 110°C for 12 minutes to obtain the printed products of Examples 14 to 17 obtained from each color ink composition.

[0073] Furthermore, on white fabrics made of 100% polyester (white polyester) and 100% cotton (white cotton), an 800g / m² finish is achieved. 2 Pretreatment solution A or B is applied in a manner to obtain a printing medium. Using an evaluation printer equipped with a printhead manufactured by SPECTRA and ink composition 13 to 20, a solid image is printed on the aforementioned printing medium. Then, the medium is heated in a conveyor oven at 110°C for 12 minutes to obtain the printed products of Examples 18 to 25 obtained from each of the respective ink compositions.

[0074] [Evaluation Method] (Evaluation of inkjet ejection performance) Continuous printing was performed using the printer described above and the water-based inkjet ink compositions of Examples 1-17 and Comparative Examples 1-9, and the ejection stability was evaluated based on the following criteria. ◎: No ejection defects were found in any of the nozzles during actual printing operations that lasted for more than one hour. 〇: In actual printing operations lasting more than 1 hour, there are nozzles with poor ejection. △: In actual printing operations that last for more than 15 minutes but less than 1 hour, there are nozzles that cannot be ejected. ×: In an actual printing operation lasting less than one hour, none of the nozzles could eject anything.

[0075] (Image density of white ink printed material) The lightness (L*) of the printed and dyed fabrics of Examples 1 to 13 and Comparative Examples 1 to 9 was measured using a spectrophotometer (product name X-Rite eXact (X-Rite Corporation)) and evaluated according to the following criteria. ◎: L* is 90 or above ○: L* is 80 or higher and less than 90 △: L* is 60 or higher and less than 80 ×: L* is less than 60

[0076] (Image density of colored ink printed materials) The optical density (OD) of the printed and dyed fabrics of Examples 14 to 17 was measured using a spectrophotometer (product name X-Rite eXact (X-Rite Corporation)) and evaluated according to the following criteria. ◎: OD is 1.0 or higher ○: OD is 0.8 or higher and less than 1.0 △: OD is 0.6 or higher and less than 0.8 ×: OD is less than 0.6

[0077] (wash fastness) The polyester and cotton fabrics of Examples 1-17 and Comparative Examples 1-9 were subjected to 10 normal washes using a household washing machine (washing conditions: normal mode wash → spin-dry → dry). The rate of change of lightness (L*) or optical density (OD) of each fabric before and after washing was measured using a spectrophotometer (product name X-Rite eXact (X-Rite Corporation)). The rate of change of lightness (L*) or optical density (OD) relative to the initial value of lightness (L*) or optical density (OD) before washing was also measured, and the results were evaluated using the following criteria. ◎: After washing, the image density retains more than 90% of the initial value. ○: After washing, the image density is above 80% and less than 90% of the initial value. △: After washing, the image density is more than 70% but less than 80% of the initial value. ×: After washing, the image density is less than 70% of the initial value.

[0078] (bleed-in) For the printed and dyed materials of Examples 18 to 25, the boundary between the printed and non-printed areas was visually confirmed, and the following criteria were used for evaluation. 〇: No color bleeding observed △: Some bleeding is visible. ×: Excessive ink bleeding prevents image formation.

[0079] [Table 1]

[0080] [Table 2]

[0081] According to Examples 1 to 17 of the present invention, which use white ink compositions and colored ink compositions, the water-based inkjet ink compositions of the present invention, when used together with a suitable pretreatment solution, exhibit excellent ejectibility and image density and wash fastness when printed on polyester and cotton fabrics. In particular, Examples 1 and 2 are identical except for the pretreatment solution. The same effect can be achieved regardless of whether formic acid or calcium formate is used. In contrast, according to Comparative Example 1, which uses a styrene-acrylic resin emulsion as the water-dispersible resin, the wash fastness is particularly insufficient for polyester and cotton fabrics. According to Comparative Example 2, which does not use a blocked isocyanate crosslinking agent, the wash fastness is particularly insufficient for cotton fabrics. Furthermore, according to Comparative Example 3, which contains an excessive amount of blocked isocyanate crosslinking agent (15% by mass × 38% by mass = 5.7% by mass), the sprayability deteriorates. Moreover, according to Comparative Examples 4 and 5, which use a non-blocked isocyanate substance as the crosslinking agent, the wash fastness is particularly insufficient for polyester and cotton fabrics. Furthermore, in Comparative Example 6, where solvent B2 is free of diols and the B1 / B2 ratio is excessively high, the wash fastness is particularly insufficient for polyester and cotton fabrics. In Comparative Example 7, where the B1 / B2 ratio is excessively low, the sprayability is insufficient. In Comparative Example 8, where solvent B2 is free of glycol ethers, the wash fastness is particularly insufficient for polyester and cotton fabrics. In Comparative Example 9, where the content of glycol ethers in solvent B2 is excessive, the sprayability is insufficient. Furthermore, examples 18-25 show examples using ink compositions 13-20. Their sprayability is excellent. However, compared to Examples 18-21 which do not contain water-based acrylic resin varnish, Examples 22-25 which contain water-based acrylic resin varnish show no bleeding into white polyester and white cotton fabrics, making them superior.

Claims

1. An ink set, characterized in that, It is composed of a pretreatment solution and a water-based inkjet ink for printing and dyeing. The pretreatment solution contains: At least one of the following: organic acid, alkali metal salt of organic acid, and alkaline earth metal salt of organic acid; and Nonionic surfactants; The water-based inkjet ink composition for printing and dyeing contains: The following are A~E: A. Pigment; B1. Solvents with a boiling point above 280℃; B2. As a solvent with a boiling point below 200°C, a diol and a diol ether comprising 0.1 to 6.0% by mass relative to the total amount of the water-based inkjet ink composition for printing and dyeing are used in the solvent with a boiling point below 200°C. Here, the mass ratio of solvent B1 to solvent B2, B1 / B2, is 0.3 to 3.0; C. Water-dispersible polyurethane resins; D. Surfactants; E. The total amount of water-based inkjet ink composition for printing and dyeing contains 0.1 to 5.0% by mass of blocked isocyanate crosslinking agent.

2. The ink assembly according to claim 1, characterized in that, The solvent B1 contains glycerol as solvent B1, and the diol B2 contains propylene glycol as solvent B2 and / or dipropylene glycol dimethyl ether as solvent B2.

3. The ink set according to claim 1 or 2, characterized in that, The water-dispersible polyurethane resin is a polyester polyurethane resin.

4. An inkjet printing method, characterized in that, The method is used for printing ink groups according to any one of claims 1 to 3, wherein the pretreatment liquid and the water-based inkjet ink composition for printing and dyeing are in contact with each other in a liquid state.

Images