Inkjet printing ink, method for manufacturing printed materials using the ink, and image-fixed articles

Abstract

To provide an ink for inkjet printing, which has, in printing by an inkjet method, excellent friction fastness of printed images and excellent discharge stability even when a heating temperature at the time of inkjet printing is low.SOLUTION: Provided is an ink for inkjet printing, comprising pigment, resin emulsion particles, an oxazoline group-containing compound, and an aqueous medium, where an average particle diameter of the resin emulsion particles is 150 nm or more, a content of the resin emulsion particles is 10 to 20 mass% relative to 100 mass% of the ink for inkjet printing, and a content of the oxazoline group-containing compound is 0.5 to 10 mass% relative to 100 mass% of the resin emulsion particles.SELECTED DRAWING: None

Description

【Technical Field】 【0001】 The present invention relates to an ink for inkjet printing, a method for producing a printed matter using the ink, and an image-fixing article. 【Background Art】 【0002】 In recent years, a printing method by an inkjet method (a method of inkjet printing to obtain a printed matter) using an ink containing a pigment as a colorant has attracted attention. For the ink used in the inkjet method, performance specific to the inkjet method such as dispersion stability, ejection stability, and fixing property to a medium is required. For an ink for inkjet printing used in the printing method by the inkjet method, in addition to the above, performance such as fastness such as rubbing fastness and washing fastness of the printed image and texture is required. Under such a background, for the purpose of providing a printing ink having excellent fastness and the like, for example, an ink containing a crosslinking agent has been proposed (for example, Patent Documents 1 and 2). In Patent Document 1, for a 100% cotton fabric, and in Patent Document 2, for a cotton fabric coated with a pretreatment liquid, it is shown in Examples that the printed matters obtained by inkjet printing each printing ink for printing have excellent fastness such as rubbing fastness. In any of the documents, heat treatment is performed at 160°C after inkjet printing. 【0003】 In Patent Document 1, in Comparative Example 7, a water-dispersible resin (resin emulsion) and an oxazoline-based compound as a crosslinking agent (2) are used, but the content of the resin emulsion particles (the content of the solid component of the resin emulsion) is 2.6% by mass, which is much lower than 10% by mass with respect to 100% by mass of the ink for inkjet printing, and the content of the oxazoline group-containing compound is 88% by mass, which is much higher than 10% by mass with respect to 100% by mass of the above resin emulsion particles. Patent Document 1 does not describe or suggest providing an ink for inkjet printing that has excellent rubbing fastness of the printed image and excellent ejection stability even when the heating temperature during inkjet printing is low in the printing by the inkjet method. 【0004】 Patent Document 2 does not describe or suggest providing an inkjet printing ink that exhibits excellent friction fastness and ejection stability of printed images, even when the heating temperature during inkjet printing is low, nor does it describe any oxazoline group-containing compounds. [Prior art documents] [Patent Documents] 【0005】 [Patent Document 1] Japanese Patent Publication No. 2009-215506 [Patent Document 2] Japanese Patent Publication No. 2011-105805 [Overview of the Initiative] [Problems that the invention aims to solve] 【0006】 In inkjet printing, heat treatment is preferably performed to fix the image during or after the image is formed by the inkjet method. However, the permissible heating temperature varies depending on the material of the fabric. Cotton can be heated up to 160°C, but many fabrics, such as polyester fibers, have lower permissible temperatures. Therefore, there is a need for the development of printing inks that offer excellent image fastness even at lower heating temperatures. Furthermore, in inkjet printing, excellent ejection stability during printing is also important from the viewpoint of reproducibility of the printed image. 【0007】 Therefore, the present invention aims to provide an inkjet printing ink that exhibits excellent friction fastness of printed images and excellent ejection stability during printing, even when the heating temperature during inkjet printing is low. [Means for solving the problem] 【0008】 The inventors focused on the above-mentioned problems and diligently studied inkjet printing inks for printing on fabrics. As a result, they discovered that in an ink containing pigment, resin emulsion particles, and an aqueous medium, by setting the particle size and amount of resin emulsion particles within a specific range and incorporating a specific amount of a specific compound, it is possible to obtain a printed image with excellent friction fastness even at low heating temperatures during inkjet printing, and an ink with excellent ejection stability during printing. This led to the completion of the present invention. 【0009】 In other words, the inkjet printing ink of the present invention is an inkjet printing ink comprising a pigment, resin emulsion particles, an oxazoline group-containing compound, and an aqueous medium, characterized in that the average particle size of the resin emulsion particles is 150 nm or more, the content of the resin emulsion particles is 10 to 20% by mass per 100% by mass of the inkjet printing ink, and the content of the oxazoline group-containing compound is 0.5 to 10% by mass per 100% by mass of the resin emulsion particles. [Effects of the Invention] 【0010】 The inkjet printing ink of the present invention, with the above-described configuration, exhibits excellent ejection stability during printing and excellent friction fastness of printed images even at low heating temperatures during inkjet printing. Therefore, by using the inkjet printing ink of the present invention in inkjet printing on fabrics, energy can be saved in the drying process, and printing (textile printing) with an image formation process that exhibits excellent friction fastness can be stably performed even on fabrics containing materials with low heat resistance, such as polyester fibers. [Modes for carrying out the invention] 【0011】 The present invention will be described in detail below. Furthermore, combinations of two or more of the individual preferred embodiments of the present invention described below are also preferred embodiments of the present invention. 【0012】 Furthermore, in this specification, "(meth)acrylate" means "acrylate" or "methacrylate," and "(meth)acrylic" means "acrylic" or "methacrylic." (Meth)acrylate may also be referred to as (meth)acrylic acid ester. 【0013】 Furthermore, in this specification, "heating temperature during inkjet printing" means the heating temperature during or after the formation of an image in an inkjet printing method using an inkjet device (inkjet printer). However, if the image is formed with the inkjet device while the fabric is heated, that is, if the heating treatment is performed while the image is being formed and no heating is performed after the image is formed, it means the heating temperature at the time of image formation. If the image is formed with the inkjet device while the fabric is heated and heating is also performed after the image is formed, it means the higher of the heating temperature at the time of image formation and the heating temperature after the image is formed. 【0014】 1. Inkjet printing ink The inkjet printing ink of the present invention is an inkjet printing ink comprising a pigment, resin emulsion particles, an oxazoline group-containing compound, and an aqueous medium, characterized in that the average particle size of the resin emulsion particles is 150 nm or more, the content of the resin emulsion particles is 10 to 20% by mass per 100% by mass of the inkjet printing ink, and the content of the oxazoline group-containing compound is 0.5 to 10% by mass per 100% by mass of the resin emulsion particles. 【0015】 The inkjet printing ink of the present invention is also referred to as the ink of the present invention. In addition to the components described above, the ink of the present invention may also contain other components as described below, if necessary. The components constituting the ink of the present invention will now be described. 【0016】 <Pigments> The ink of the present invention contains a pigment. Examples of pigments include organic pigments and inorganic pigments, which may be used individually or in combination of two or more types. Furthermore, if necessary, these may be used in combination with extender pigments. 【0017】 Examples of organic pigments include azo pigments such as benzidine and Hansa Yellow, diazo pigments, azomethine pigments, methine pigments, anthraquinone pigments, phthalocyanine pigments such as phthalocyanine blue, perinone pigments, perylene pigments, diketopyrrolopyrrole pigments, thioindigo pigments, isoindolinone pigments such as iminoisoindoline pigments and iminoisoindolinone, dioxazine pigments, quinacridone pigments such as quinacridone red and quinacridone violet, flavanthron pigments, indanthron pigments, anthrapyrimidine pigments, carbazole pigments, monoallylide yellow, diallylide yellow, benzimimidazolone yellow, toryl orange, naphthol orange, and quinophthalone pigments. The hue is not particularly limited, and any chromatic pigment such as yellow, magenta, cyan, blue, red, orange, and green can be used. Specific examples include product codes such as CI Pigment Yellow, CI Pigment Red, CI Pigment Orange, CI Pigment Violet, CI Pigment Blue, and CI Pigment Green. When targeting polypropylene fabrics, it is preferable to use metal-free pigments as organic pigments to avoid promoting the thermal decomposition of polypropylene. Specifically, pigment blue 16 can be selected. 【0018】 Examples of inorganic pigments include titanium dioxide, antimony trioxide, zinc oxide (such as zinc oxide), lithopone, lead white, red iron oxide, black iron oxide, chromium green oxide, carbon black, lead yellow, molybdenum red, ferric ferrocyanide (Prussian blue), ultramarine, and lead chromate. Other examples of inorganic pigments include flattened pigments such as mica, clay, aluminum powder, talc, and aluminum silicate, as well as extender pigments such as calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, and magnesium carbonate. Furthermore, examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black. Among inorganic pigments, titanium dioxide, antimony trioxide, zinc oxide (such as zinc oxide), lithopone, lead white, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, magnesium carbonate, clay, talc, and aluminum silicate are preferred as white pigments. Titanium dioxide is preferred from the viewpoint of having a high refractive index and excellent opacity. Among titanium dioxide, titanium dioxide with a rutile crystal structure is preferred. Preferred coloring pigments include the above-mentioned organic pigments, red iron oxide, black iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, ferric ferrocyanide (Prussian blue), ultramarine, and lead chromate. 【0019】 The average particle size of the pigment is preferably 10 to 1000 nm, and more preferably 20 to 500 nm, from the viewpoint of dispersion stability and color development or opacity. In the case of white pigments, the average particle size is preferably 100 to 500 nm from the viewpoint of superior opacity, more preferably 150 nm or more at the lower limit, even more preferably 200 nm or more, and more preferably 450 nm or less at the upper limit, even more preferably 400 nm or less. In the case of a coloring pigment, the average particle diameter is preferably 20 to 200 nm, more preferably 40 nm or more, still more preferably 50 nm or more from the viewpoint of color development, and for the upper limit, more preferably 150 nm or less, still more preferably 100 nm or less. 【0020】 The average particle diameter of the above pigment is the average particle diameter in the ink of the present invention. The average particle diameter of the pigment can be measured by a laser diffraction scattering type particle size distribution analyzer or a dynamic light scattering method. For example, the value obtained by the cumulant method when measured using a particle size distribution measuring instrument based on dynamic light scattering (manufactured by Otsuka Electronics Co., Ltd., product number: FPAR-1000) can be adopted. However, when it is difficult to measure by the dynamic light scattering method, such as in the case of a black pigment, the 50% particle diameter in the volume-based particle size distribution obtained by measurement with a laser diffraction scattering type particle size distribution analyzer can be adopted as the average particle diameter. 【0021】 The pigment is preferably dispersed and stabilized in the ink of the present invention with a dispersant. Examples of the above dispersant include poly(meth)acrylic acid (salt) such as poly(meth)acrylic acid and poly(meth)acrylate; a copolymer of (meth)acrylic acid (salt) and one or more ethylenically unsaturated double bond-containing monomers such as (meth)acrylic acid ester, (meth)acrylonitrile, (meth)acrylamide, styrene, maleic acid, maleic anhydride, maleic acid ester, vinyl acetate; polyvinyl alcohol; polyvinyl pyrrolidone and the like. 【0022】 <Resin emulsion particles> The resin emulsion particles contained in the ink of the present invention will be described. The above resin emulsion particles are not particularly limited, but resin particles derived from an aqueous emulsion are preferred. 【0023】 The shape of the above resin emulsion particles is not particularly limited, but is usually spherical. The shape can be measured by a transmission electron microscope or a scanning electron microscope. The average particle size of the resin emulsion particles is 150 nm or larger. By setting the average particle size to 150 nm or larger, it becomes easier to incorporate resin emulsion particles at a high concentration while maintaining the viscosity of the ink within an appropriate range. The average particle size is more preferably 180 nm or larger, even more preferably greater than 200 nm, and even more preferably 210 nm or larger. On the other hand, there is no particular upper limit, but it is preferably 350 nm or smaller, more preferably 330 nm or smaller, and even more preferably 300 nm or smaller. In this specification, the average particle size of the resin emulsion particles is the value obtained by the cumulant method when measured using a particle size distribution analyzer that uses dynamic light scattering (manufactured by Otsuka Electronics Co., Ltd., product number: FPAR-1000). 【0024】 The glass transition temperature of the resin emulsion particles is not particularly limited, but from the viewpoint of ensuring that the printed material obtained using the ink of the present invention has a superior texture, it is preferably 0°C or lower. More preferably -10°C or lower, and even more preferably -15°C or lower. On the other hand, the lower limit is not particularly limited, but -50°C or higher is preferred, and -40°C or higher is more preferred. 【0025】 The glass transition temperature can be obtained by differential scanning calorimetry (DSC), differential calorimetry (DTA), or thermomechanical analysis (TMA), but it is preferable to use the value obtained by differential scanning calorimetry (DSC). Unless otherwise specified, the glass transition temperature in this specification refers to the value obtained by differential scanning calorimetry (DSC). 【0026】 However, if the glass transition temperature can be calculated using Fox's formula based on the composition of the resin components in the resin emulsion particles described later, such as vinyl resins, (meth)acrylic resins, and acrylic-styrene polymers, then this can be used instead. 【0027】 Examples of differential scanning calorific value measuring devices include the DSC220C, manufactured by Seiko Instruments Inc. Furthermore, there are no particular limitations on the methods used when measuring differential scanning calorific value, such as the method for plotting the differential scanning calorific value (DSC) curve, the method for obtaining the first derivative curve from the DSC curve, the method for performing smoothing, or the method for determining the target peak temperature. For example, when using the aforementioned measuring device, the graph can be created from the data obtained using the device. In this case, analysis software capable of performing mathematical processing can be used. Examples of such analysis software include the EXSTAR6000 analysis software (manufactured by Seiko Instruments Inc.). Preferably, the measurement conditions are a heating rate of 15°C / min and a cooling rate of 15°C / min, and the values ​​obtained under these conditions should be adopted. Furthermore, in the above measurement, the onset temperature, intermediate temperature, inflection point temperature, and termination temperature of the glass transition are observed, and the intermediate temperature is defined as the glass transition temperature (Tg) of the resin emulsion particles. 【0028】 Fox's formula is as follows: 1 / Tg = Σ(Wm / Tgm) / 100 In the formula, Tg is the glass transition temperature, Wm is the content (mass%) of monomer m in the monomer components constituting the resin component, and Tgm is the glass transition temperature (absolute temperature: K) of the monomer m homopolymer. 【0029】 The glass transition temperature can be determined by substituting the content of each monomer relative to the total amount of monomers used to form the resin constituting the resin emulsion particles, and the glass transition temperature of each monomer's homopolymer into the above formula. Examples of homopolymers that can be used in the above method are 95°C for acrylic acid homopolymer, 130°C for methacrylic acid homopolymer, 105°C for methyl methacrylate homopolymer, 100°C for styrene homopolymer, 83°C for cyclohexyl methacrylate homopolymer, 20°C for n-butyl methacrylate homopolymer, -70°C for 2-ethylhexyl acrylate homopolymer, -56°C for n-butyl acrylate homopolymer, 55°C for hydroxyethyl methacrylate homopolymer, 165°C for acrylamide homopolymer, and 130°C for 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine homopolymer. 【0030】 The above resin emulsion particles preferably have acidic functional groups. Among acidic functional groups, carboxyl groups (-COOH) are preferred. The content of acidic functional groups is preferably 0.06 to 3% by mass per 100% by mass of resin emulsion particles. Furthermore, the content of acidic functional groups is preferably 0.1 to 5% by mass, expressed as the content of constituent units derived from monomers having acidic functional groups per 100% by mass of resin emulsion particles. The preferred content of carboxyl groups is the same as that for acidic functional groups. 【0031】 By setting the content of carboxyl groups and acidic functional groups in the resin emulsion particles within the above ranges, when used as an ink, it is possible to achieve excellent image uniformity in printed images and excellent wash fastness of printed images, even at low heating temperatures during inkjet printing. The content of acidic functional groups such as carboxyl groups in the resin emulsion particles can be adjusted, for example, by adjusting the composition of the monomers used in the polymerization of the resin emulsion particles. 【0032】 The acid value of the above resin emulsion particles is preferably 0.5 to 50 mg KOH / g. More preferably, it is 0.8 to 40 mg KOH / g. The preferred range for the acid value derived from the carboxyl groups in the above resin emulsion particles is the same as for the above acid value. By setting the acid value of the resin emulsion particles and the acid value derived from the carboxyl groups within the above ranges, the image uniformity of the image obtained using the ink of the present invention and the wash fastness of the obtained image can be made excellent, even when the heating temperature during inkjet printing is low. 【0033】 The weight-average molecular weight of the resin component constituting the above-mentioned resin emulsion particles is preferably 50,000 or more, more preferably 300,000 or more, even more preferably 550,000 or more, and particularly preferably 600,000 or more, from the viewpoint of further improving water resistance and adhesion. The upper limit of the weight-average molecular weight of the resin component is preferably 5,000,000 or less, from the viewpoint of improving film-forming ability and water resistance. The weight-average molecular weight mentioned above refers to the weight-average molecular weight (polystyrene equivalent) measured using gel permeation chromatography [manufactured by Tosoh Corporation, catalog number: HLC-8120GPC, columns: TSKgel G-5000HXL and TSKgel GMHXL-L used in series]. 【0034】 The structure of the resin emulsion particles described above is not particularly limited; it may be a form in which the composition of the entire particle is uniform, or it may be a core-shell structure consisting of a core and a shell with different compositions and / or physical properties. The core-shell structure is not limited to two layers, but may consist of three or more layers. Among these, a form with two or more layers of core-shell structure that can improve the balance between the elongation and hardness of the coating film is preferred. 【0035】 The resin emulsion particles described above are preferably dispersed and stabilized with a surfactant. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and conventionally known surfactants. These surfactants may be used individually or in combination of two or more types. 【0036】 Among the surfactants mentioned above, nonionic surfactants or anionic surfactants are preferred. Surfactants containing polymerizable groups in their molecules are also preferred. Examples of polymerizable groups include groups having ethylenically unsaturated double bonds. Among the surfactants mentioned above, nonionic surfactants containing polymerizable groups or anionic surfactants containing polymerizable groups are particularly preferred. Surfactants containing polymerizable groups are also referred to as reactive emulsifiers. High molecular weight emulsifiers can also be used as surfactants. 【0037】 Examples of anionic surfactants include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate, and sodium alkyldiphenyl ether disulfonate; alkylaryl sulfonate salts such as ammonium dodecylbenzene sulfonate and sodium dodecylnaphthalene sulfonate; polyoxyethylene alkyl sulfonate salts; polyoxyethylene alkyl sulfate salts; polyoxyethylene alkylaryl sulfate salts; dialkyl sulfosuccinates; and aryl sulfonic acid-formaldehyde condensates. Examples include, but are not limited to, fatty acid salts such as ammonium laurylate and sodium stearate; sulfate esters or salts thereof having an allyl group, such as bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkyl sulfosuccinate salt, (meth)acrylate polyoxyethylene sulfonate salt, (meth)acrylate polyoxyethylene phosphate salt, and sulfonate salt of allyloxymethylalkyloxypolyoxyethylene; sulfate ester salts of allyloxymethyl alkoxyethyl polyoxyethylene, polyoxyalkylene alkenyl ether sulfate ammonium salt, etc. 【0038】 Examples of nonionic surfactants include, but are not limited to, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, condensates of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, condensation products of ethylene oxide and aliphatic amines, and polyoxyalkylene alkenyl ethers. 【0039】 Examples of cationic surfactants include alkylammonium salts such as dodecylammonium chloride, but are not limited to these examples. Examples of amphoteric surfactants include betaine ester type emulsifiers, but are not limited to these examples. 【0040】 Examples of polymer emulsifiers include, but are not limited to, poly(meth)acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl (meth)acrylates such as polyhydroxyethyl acrylate; and copolymers in which one or more monomers constituting these polymers are copolymerized components. 【0041】 Examples of reactive emulsifiers include propenyl-alkyl sulfosuccinate salts, (meth)acrylate polyoxyethylene sulfonate salts, (meth)acrylate polyoxyethylene phosphate salts (e.g., Sanyo Chemical Industries, Ltd., trade name: Eleminol RS-30, etc.), polyoxyethylene alkylpropenylphenyl ether sulfonate salts (e.g., Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10, etc.), allyloxymethylalkyloxypolyoxyethylene sulfonate salts (e.g., Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.), polyoxyethylene styrene-propenylphenyl ether sulfate ammonium (e.g., Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon AR-10, etc.), polyoxyethylene styrene-propenylphenyl ether (e.g., Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon AN-10, etc.), allyloxymethylnonylphenoxyethyl hydroxypolyoxy Examples include ethylene sulfonate salts (e.g., ADEKA Corporation, product name: Adekarya Soap SE-10), allyloxymethyl alkoxyethyl hydroxypolyoxyethylene sulfate salts (e.g., ADEKA Corporation, product names: Adekarya Soap SR-10, SR-30), bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salts (e.g., Nippon Emulsifier Co., Ltd., product name: Antox MS-60), allyloxymethyl alkoxyethyl hydroxypolyoxyethylene (e.g., ADEKA Corporation, product name: Adekarya Soap ER-20), polyoxyethylene alkylpropenylphenyl ethers (e.g., Daiichi Kogyo Seiyaku Co., Ltd., product name: Aqualon RN-20), and allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene (e.g., ADEKA Corporation, product name: Adekarya Soap NE-10), but are not limited to these examples. 【0042】 The resin constituting the above resin emulsion particles is not particularly limited, and examples include vinyl resins, (meth)acrylic resins, olefin resins, urethane resins, fluororesins, silicone resins, epoxy resins, phenoxy resins, phenolic resins, xylene resins, and the like. 【0043】 In particular, polymers obtained by polymerizing ethylenically unsaturated double-bond-containing monomers are preferred. In other words, polymers containing constituent units derived from ethylenically unsaturated double-bond-containing monomers are preferred. When the resin is a polymer obtained by polymerizing ethylenically unsaturated double-bond-containing monomers, the content of acidic functional groups such as carboxyl groups and hydrophobic monomers can be arbitrarily designed. 【0044】 Examples of ethylenically unsaturated double bond-containing monomers include vinyl monomers such as vinyl acetate, vinyl chloride, acrylonitrile, acrylamide, and vinyl benzoate; (meth)acrylic monomers such as (meth)acrylic acid esters and (meth)acrylic acid; styrene monomers such as styrene, α-methylstyrene, and chloromethylstyrene; olefin monomers such as ethylene and propylene; and others, as well as maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, monomethyl maleic acid, monobutyl maleic acid, monomethyl itaconic acid, and monobutyl itaconic acid. 【0045】 As the resin constituting the above resin emulsion particles, a (co)polymer obtained by (co)polymerizing one or more of these monomers is preferred. Examples include vinyl acetate polymer, vinyl chloride polymer, ethylene-vinyl acetate copolymer, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-ethylene-styrene copolymer, acrylonitrile-chlorinated ethylene-styrene copolymer, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate-(meth)acrylic acid ester copolymer, (meth)acrylic acid ester (co)polymer, (meth)acrylic acid ester-(meth)acrylic acid copolymer, (meth)acrylic acid ester-styrene copolymer, (meth)acrylic acid ester-(meth)acrylic acid-styrene copolymer, ethylene-vinyl acetate-(meth)acrylic acid ester copolymer, (meth)acrylic acid ester-urethane copolymer, acrylonitrile-(meth)acrylic acid ester-styrene copolymer, etc. 【0046】 In particular, from the viewpoint of easily obtaining printed materials that are not only excellent in friction fastness to fabrics mainly composed of highly hydrophobic fibers such as polypropylene fibers, but also have excellent texture, copolymers obtained by copolymerizing a monomer composition containing at least one or more (meth)acrylic monomers and one or more styrene monomers as ethylenically unsaturated double bond-containing monomers are preferred. Such copolymers will also be called acrylic-styrene polymers. Examples of the above acrylic-styrene polymers include (meth)acrylic acid ester-styrene copolymers, (meth)acrylic acid ester-(meth)acrylic acid-styrene copolymers, acrylonitrile-(meth)acrylic acid ester-styrene copolymers, and the like. 【0047】 The monomers used to form the above acrylic-styrene polymer may include monomers other than (meth)acrylic monomers and styrene monomers. However, the total content of (meth)acrylic monomers and styrene monomers relative to 100% by mass of the total monomers used to form the above acrylic-styrene polymer is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass. 【0048】 In other words, the above acrylic-styrene polymer only needs to contain constituent units derived from (meth)acrylic monomers and constituent units derived from styrene monomers, and may also contain other constituent units. However, the total content of constituent units derived from (meth)acrylic monomers and styrene monomers, relative to 100% by mass of the total constituent units of the above acrylic-styrene polymer, is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass. 【0049】 As the (meth)acrylic monomer mentioned above, one or more of the conventionally known (meth)acrylic acid esters and (meth)acrylic acid can be selected and used. 【0050】 Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, tridecyl (meth)acrylate, and cyclohexyl (meth)acrylate. Alkyl (meth)acrylates such as lylate, n-lauryl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate; fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate; benzyl (meth)acrylate, phenylethyl (meth)acrylate, methylbenzyl (meth)acrylate Aralkyl (meth)acrylates such as naphthylmethyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate; alkoxyalkyl group-containing (meth)acrylates such as methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, trimethylolpropane tripoxy (meth)acrylate; silyl group-containing (meth)acrylates such as γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropylhydroxysilane, γ-(meth)acryloyloxypropylmethylhydroxysilane;Carbonyl group-containing (meth)acrylates such as (meth)acryloyl aziridine, 2-aziridinylethyl methacrylate, 2-(acetoacetoxy)ethyl methacrylate; carbonyl group-containing (meth)acrylates such as (meth)acryloyl aziridine, 2-aziridinylethyl methacrylate; ethylene glycol (meth)acrylate, ethylene Examples include oxo-group-containing (meth)acrylates such as diethylene glycol (meth)acrylate, diethylene glycol (meth)acrylate, and diethylene glycol methoxy(meth)acrylate; and piperidine-group-containing (meth)acrylates such as 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine and 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine. One or more of these can be selected and used. 【0051】 As (meth)acrylic acid esters, polyfunctional (meth)acrylates can also be used. Examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and propylene oxide-modified neopentyl glycol di(meth)acrylate. Di(meth)acrylates of polyhydric alcohols with 1 to 10 carbon atoms, such as tripropylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate with 2 to 50 moles of ethylene oxide added; polypropylene glycol di(meth)acrylate with 2 to 50 moles of propylene oxide added; alkyl di(meth)acrylates with 2 to 50 moles of alkylene oxide groups with 2 to 4 carbon atoms, such as tripropylene glycol di(meth)acrylate; ethoxylated Tri(meth)acrylates of polyhydric alcohols with 1 to 10 carbon atoms, such as ricerin tri(meth)acrylate, propylene oxide-modified glycerol tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol monohydroxytri(meth)acrylate, and trimethylolpropane triethoxytri(meth)acrylate; pentaerythritol tetra(meth)acrylate, dipenta Tetra(meth)acrylates of polyhydric alcohols with 1 to 10 carbon atoms, such as erythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; penta(meth)acrylates of polyhydric alcohols with 1 to 10 carbon atoms, such as pentaerythritol penta(meth)acrylate and dipentaerythritol (monohydroxy)penta(meth)acrylate; hexa(meth)acrylates of polyhydric alcohols with 1 to 10 carbon atoms, such as pentaerythritol hexa(meth)acrylate;Examples include epoxy group-containing (meth)acrylates such as bisphenol A di(meth)acrylate, 2-(2'-vinyloxyethoxyethyl)(meth)acrylate, and epoxy(meth)acrylate; and polyfunctional (meth)acrylates such as urethane(meth)acrylate. As the (meth)acrylic acid, acrylic acid and methacrylic acid are preferred. 【0052】 Examples of the styrene monomers mentioned above include styrene, α-methylstyrene, and p-methyl Styrene, tert-methylstyrene, chlorostyrene, vinyltoluene, 2-styryl Examples include ethyltrimethoxysilane. Styrene monomers may have functional groups on the benzene ring, such as methyl groups, alkyl groups such as tert-butyl groups, nitro groups, nitrile groups, alkoxyl groups, acyl groups, sulfone groups, hydroxyl groups, and halogen atoms. Among styrene monomers, styrene is preferred from the viewpoint of improving water resistance. As the styrene monomer mentioned above, a polyfunctional styrene monomer can also be used. Divinylbenzene is a preferred example of the polyfunctional styrene monomer. 【0053】 The content of styrene monomers in the monomers for forming the above-mentioned acrylic-styrene polymer is preferably 1 to 55% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 45% by mass, based on 100% by mass of the total amount of (meth)acrylic monomers and styrene monomers. By setting the content of styrene monomers within the above range, it becomes easier to obtain printed materials with superior texture or wash fastness. 【0054】 The above acrylic-styrene polymer is preferably a polymer obtained by copolymerizing the above (meth)acrylic monomer and the above styrene monomer with a monomer composition having a composition ratio within the above range. 【0055】 The above acrylic-styrene polymer is preferably a polymer having carboxyl groups, and the carboxyl group content is preferably 0.06 to 3% by mass per 100% by mass of resin emulsion particles. Furthermore, the carboxyl group content is preferably 0.1 to 5% by mass, expressed as the content of constituent units derived from monomers having carboxyl groups per 100% by mass of resin emulsion particles. 【0056】 Furthermore, it is preferable that the carboxyl group is a carboxyl group derived from (meth)acrylic acid. Therefore, it is preferable that the constituent units derived from the (meth)acrylic monomer constituting the acrylic-styrene polymer include one or more constituent units derived from (meth)acrylic acid, and it is even more preferable that they include one or more constituent units derived from the (meth)acrylate ester and one or more constituent units derived from (meth)acrylic acid. 【0057】 The content of the (meth)acrylic acid-derived constituent units constituting the above acrylic-styrene polymer is preferably 0.1 to 5% by mass, more preferably 0.2 to 4% by mass, and even more preferably 1 to 3% by mass, based on 100% by mass of the total amount of constituent units derived from (meth)acrylic monomers and styrene monomers. 【0058】 The (meth)acrylic monomer for forming the above acrylic-styrene polymer preferably contains one or more (meth)acrylic acids, and more preferably contains one or more (meth)acrylate esters and one or more (meth)acrylic acids. 【0059】 The (meth)acrylic acid content in the monomers for forming the above acrylic-styrene polymer is preferably 0.1 to 5% by mass, more preferably 0.2 to 4% by mass, and even more preferably 1 to 3% by mass, based on 100% by mass of the total amount of (meth)acrylic monomers and styrene monomers. 【0060】 The (meth)acrylic monomer used to form the above acrylic-styrene polymer preferably contains (meth)acrylic acid esters in addition to (meth)acrylic acid. Among the (meth)acrylic acid esters, it is preferable to contain one or more alkyl (meth)acrylates, and it is also preferable to contain one or more hydroxyalkyl (meth)acrylates. Furthermore, it is more preferable to contain one or more alkyl (meth)acrylates and one or more hydroxyalkyl (meth)acrylates. 【0061】 Among the alkyl (meth)acrylates mentioned above, it is preferable to include alkyl (meth)acrylates having 1 to 18 carbon atoms in the alkyl group, and it is even more preferable to include alkyl (meth)acrylates having 4 to 12 carbon atoms in the alkyl group. Furthermore, it is also preferable to use two or more alkyl (meth)acrylates with different numbers of carbon atoms in combination. For example, this includes a combination of alkyl (meth)acrylates having 1 to 5 carbon atoms and alkyl (meth)acrylates having 6 to 18 carbon atoms, a combination of alkyl (meth)acrylates having 1 carbon atom and alkyl (meth)acrylates having 8 to 18 carbon atoms, a combination of alkyl (meth)acrylates having 1 carbon atom, alkyl (meth)acrylates having 4 to 6 carbon atoms and alkyl (meth)acrylates having 8 to 18 carbon atoms, and a combination of alkyl (meth)acrylates having 2 to 6 carbon atoms and alkyl (meth)acrylates having 8 to 12 carbon atoms. Furthermore, as the hydroxyalkyl (meth)acrylate, a hydroxyalkyl (meth)acrylate having 1 to 18 carbon atoms in the hydroxyalkyl chain is more preferred, and a hydroxyalkyl (meth)acrylate having 2 to 4 carbon atoms is even more preferred. 【0062】 Furthermore, the monomers used to form the above-mentioned acrylic-styrene polymer may include monomers other than (meth)acrylic monomers and styrene monomers. Examples of other monomers include acrylonitrile, vinyl acetate, and acrylamide. In addition, examples of other monomers include addition polymerizable oxazolines. Examples of addition polymerizable oxazolines include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. 【0063】 The above acrylic-styrene polymer is preferably obtained by copolymerizing the above preferred monomers in a preferred proportion, and is preferably a polymer that contains constituent units derived from the preferred monomers in a proportion corresponding to the preferred monomer blending ratio. 【0064】 The resin emulsion particles constituting the ink of the present invention preferably contain the above-mentioned acrylic-styrene polymer as the main component of the resin. These particles are also referred to as acrylic-styrene polymer emulsion particles. 【0065】 While preferred embodiments of the resin emulsion particles constituting the ink of the present invention have been described regarding particle shape, average particle size, glass transition temperature, acidic functional group content, carboxyl group content, acid value, weight-average molecular weight, particle structure, surfactant, etc., all of these can be directly applied to the above-mentioned acrylic-styrene polymer emulsion particles. 【0066】 The above-mentioned acrylic-styrene polymer emulsion particles can be produced by conventionally known emulsion polymerization methods. The preferred types, combinations, and blending ratios of monomers used in emulsion polymerization are similar to those described for the monomers used to form the above-mentioned acrylic-styrene polymer. Specifically, the above-mentioned acrylic-styrene polymer emulsion particles can be produced by emulsion polymerization of monomers, including (meth)acrylic monomers, styrene monomers, and optionally other ethylenically unsaturated double-bond-containing monomers, in an aqueous medium in the presence of an emulsifier. Conventionally known emulsifiers can also be used. The above-mentioned surfactant can be used as the emulsifier, and its preferred embodiment is the same as that for the surfactant described above. 【0067】 Furthermore, in the emulsion obtained by the above emulsion polymerization method, it is preferable that the residual monomer is less than 100 ppm by mass relative to the emulsion. The residual monomer can be measured by gas chromatography or the like. It is preferable to add an additional polymerization initiator to extend the maturation period so that the residual monomer is less than 100 ppm after the polymerization reaction has matured. 【0068】 <Oxazoline group-containing compounds> The ink of the present invention contains an oxazoline group-containing compound. In the present invention, an oxazoline group-containing compound means a compound having two or more oxazoline groups in its molecule. Examples of the above oxazoline group-containing compounds are 2,2'-bis(2-oxazoline), 2,2'-methylene-bis(2-oxazoline), 2,2'-ethylene-bis(2-oxazoline), 2,2'-trimethylene-bis(2-oxazoline), 2,2'-tetramethylene-bis(2-oxazoline), 2,2'-hexamethylene-bis(2-oxazoline), 2,2'-octamethylene-bis(2-oxazoline), and 2,2'-ethylene-bis Examples include (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(4,4'-dimethyl-2-oxazoline), bis(2-oxazolinylcyclohexane) sulfide, bis(2-oxazolinylnorbornane) sulfide, and oxazoline group-containing polymers, but are not limited to these examples. These oxazoline group-containing compounds may be used individually or in combination of two or more types. 【0069】 Among the oxazoline group-containing compounds mentioned above, water-soluble oxazoline group-containing compounds are preferred from the viewpoint of excellent crosslinking performance, and oxazoline group-containing polymers are also preferred. The oxazoline group-containing polymer can be produced by conventionally known production methods. For example, one method can be used to polymerize one or more addition-polymerizable oxazolines, or a monomer component containing an addition-polymerizable oxazoline and a monomer copolymerizable with addition-polymerizable oxazolines. As the copolymerizable monomer, a monomer that does not have a functional group that reacts with the oxazoline group and is copolymerizable with the addition-polymerizable oxazoline is preferred. For example, a monomer that does not have a functional group that reacts with the oxazoline group in the ethylenically unsaturated double-bond-containing monomer mentioned above can be cited. Examples include vinyl monomers such as vinyl acetate, vinyl chloride, acrylonitrile, acrylamide, and vinyl benzoate; (meth)acrylic monomers such as (meth)acrylic acid esters; styrene monomers such as styrene, α-methylstyrene, and chloromethylstyrene; and olefin monomers such as ethylene and propylene. 【0070】 Examples of the above-mentioned addition polymerizable oxazolines include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. 【0071】 Among oxazoline group-containing polymers, water-soluble oxazoline group-containing polymers are preferred and can be produced by the same method as the above-mentioned method for producing oxazoline group-containing polymers. Examples of the above-mentioned water-soluble oxazoline group-containing polymers include polymers that have an acrylic polymer, an acrylic-styrene polymer, etc. as the main chain and contain oxazoline groups in the side chains. 【0072】 Commercially available polymers containing oxazoline groups can also be used. Examples include water-soluble polymers such as Epocross WS-500 and Epocross WS-700 manufactured by Nippon Shokubai Co., Ltd., and emulsion-type polymers such as Epocross K-2010, Epocross K-2020, and Epocross K-2030. Among these, water-soluble polymers such as Epocross WS-500 and Epocross WS-700 manufactured by Nippon Shokubai Co., Ltd. are preferred. 【0073】 The content of the oxazoline group-containing compound in the ink of the present invention is 0.5 to 10% by mass per 100% by mass of the resin emulsion particles. This range is preferred mainly from the viewpoint of friction fastness. The above content is preferably 5% by mass or less. 【0074】 It is presumed that the oxazoline group-containing compound described above exerts a crosslinking agent-like effect even at low temperatures, forming a tough coating film, through interaction with or chemical reactions with components contained in the ink of the present invention, such as resin emulsion particles, pigments, or pigment dispersants. 【0075】 <Aqueous medium> The ink of the present invention contains an aqueous medium. In the present invention, the aqueous medium means a solvent containing water. The water content in the aqueous medium is preferably 10 to 100% by mass. More preferably 25% by mass or more, even more preferably 60% by mass or more, and particularly preferably 90% by mass or more. The remainder is preferably an organic solvent. 【0076】 The above aqueous medium may contain an organic solvent. Examples of organic solvents include glycols such as propylene glycol, 1,3-propanediol, glycerin, dipropylene glycol, tripropylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; monoethylene glycol ethers such as monoethylene glycol monomethyl ether, monoethylene glycol monoethyl ether, monoethylene glycol monopropyl ether, monoethylene glycol monoisopropyl ether, monoethylene glycol monobutyl ether, and monoethylene glycol monoisobutyl ether; monopropylene glycol monomethyl ether, monopropylene glycol monoethyl ether, monopropylene glycol monopropyl ether, monopropylene glycol monoisopropyl ether, and monopropyl ether. Monopropylene glycol ethers such as propylene glycol monobutyl ether and monopropylene glycol monoisobutyl ether; polyethylene glycol ethers such as polyethylene glycol monomethyl ether (moles of EO added = 2-10, preferably 2-4), polyethylene glycol monoethyl ether (moles of EO added = 2-10, preferably 2-4), polyethylene glycol monopropyl ether (moles of EO added = 2-10, preferably 2-4), polyethylene glycol monoisopropyl ether (moles of EO added = 2-10, preferably 2-4), polyethylene glycol monobutyl ether (moles of EO added = 2-10, preferably 2-4), and polyethylene glycol monoisobutyl ether (moles of EO added = 2-10, preferably 2-4);Examples include polypropylene glycol ethers such as monomethyl ether of polypropylene glycol (number of EO added moles = 2 to 10, preferably 2 to 4), monoethyl ether of polypropylene glycol (number of EO added moles = 2 to 10, preferably 2 to 4), monopropyl ether of polypropylene glycol (number of EO added moles = 2 to 10, preferably 2 to 4), monoisopropyl ether of polypropylene glycol (number of EO added moles = 2 to 10, preferably 2 to 4), monobutyl ether of polypropylene glycol (number of EO added moles = 2 to 10, preferably 2 to 4), and monoisobutyl ether of polypropylene glycol (number of EO added moles = 2 to 10, preferably 2 to 4), as well as heterocyclic compounds such as 2-pyrrolidone and N-methyl-2-pyrrolidone. 【0077】 Among these, propylene glycol, glycerin, diethylene glycol, triethylene glycol, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monobutyl ether, polyethylene glycol (moles of EO added = 2-4) monobutyl ether, and 2-pyrrolidone are preferred, and more preferably propylene glycol, triethylene glycol, polyethylene glycol (moles of EO added = 2-4) monobutyl ether, and 2-pyrrolidone. These organic solvents may be used individually or in combination of two or more. 【0078】 <Composition ratio> The resin emulsion particle content in the ink of the present invention is 10 to 20% by mass per 100% by mass of ink. This range is preferred from the viewpoint of improving the friction fastness of images processed at low temperatures during inkjet printing and the stability of ink ejection during printing. Preferably, it is 10.5% by mass or more and 18% by mass or less. The pigment content in the ink of the present invention is not particularly limited, but is preferably 1 to 20% by mass per 100% by mass of ink. Below 1% by mass there is a risk of insufficient color development and opacity, and above 20% by mass there is a risk of a decrease in texture. More preferably it is 2% by mass or more and 18% by mass or less. The aqueous medium content in the ink of the present invention is preferably 55 to 89% by mass, and more preferably 70 to 85% by mass, based on 100% by mass of the ink of the present invention. In the ink of the present invention, the pigment content relative to 100% by mass of the total content of the pigment, resin emulsion particles, and oxazoline group-containing compound is preferably 10 to 80% by mass, and more preferably 15 to 75% by mass, from the viewpoint of improving the opacity or colorability of the formed or printed image. 【0079】 <Other ingredients> The ink of the present invention may contain other components besides the essential components (pigment, resin emulsion particles, aqueous medium) described above, to the extent that the objectives of the present invention are not hindered. For example, appropriate amounts of additives such as surfactants, dispersants, leveling agents, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, defoamers, dyes, antioxidants, crosslinking accelerators, pH adjusters, and preservatives may be included. As the leveling agent, it is preferable to use, for example, acetylene glycol-based, silicone-based, or fluorine-based surfactants, and among these, polyether-modified silicone compounds are preferred. 【0080】 When adding the above-mentioned other components, their content is not particularly limited, but is preferably 2% by mass or less, and preferably 1% by mass or less, relative to 100% by mass of the ink of the present invention. Furthermore, to exhibit the additive effect, it is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more. 【0081】 <Method for manufacturing inkjet printing ink according to the present invention> The method for producing the ink of the present invention is not particularly limited. For example, it can be produced by mixing a pigment, resin emulsion particles, an oxazoline group-containing compound, and an aqueous medium, but preferred production examples are shown. 【0082】 First, an emulsion containing resin emulsion particles and a pigment dispersion are prepared. The pigment dispersion is preferably one in which the pigment is dispersed in an aqueous medium. The pigment dispersion can be produced, for example, by mixing the pigment and a dispersant in an aqueous medium such as water and performing a dispersion treatment using a bead mill or the like. The pigment content in the pigment dispersion is not particularly limited, but is preferably 15 to 65% by mass relative to 100% by mass of the pigment dispersion. On the other hand, the emulsion containing resin emulsion particles can be produced by a conventionally known emulsion polymerization method as described above. The resin emulsion particle content in the emulsion is not particularly limited, but is preferably 30 to 65% by mass relative to 100% by mass of the emulsion. The emulsion obtained by the emulsion polymerization method usually contains emulsifiers such as surfactants used for emulsification, but this emulsion may be used as is to prepare the ink of the present invention. 【0083】 Next, the pigment dispersion, emulsion, oxazoline group-containing compound, and an aqueous medium as needed are mixed. For mixing, the oxazoline group-containing compound may be used as is, or a solution diluted with an aqueous medium may be used. The method and order of mixing the above components are not particularly limited. For example, the emulsion and pigment dispersion may be mixed first, and then the oxazoline group-containing compound may be mixed; the pigment dispersion and the oxazoline group-containing compound may be mixed first, and then the emulsion may be mixed; the emulsion and the oxazoline group-containing compound may be mixed first, and then the pigment dispersion may be mixed; or the pigment dispersion, emulsion, and oxazoline group-containing compound may be mixed almost simultaneously. 【0084】 Furthermore, for the purpose of adjusting the concentration of each component in the ink of the present invention or adjusting the physical properties of the ink, an aqueous medium or water or organic solvent constituting the aqueous medium may be mixed, either individually or in combination, or other additives may be further mixed. The timing of mixing these (aqueous medium, additives, etc.) can be selected as appropriate. In addition, centrifugation or filter filtration may be performed as necessary. 【0085】 By the manufacturing method described above, the ink of the present invention is obtained, which comprises a pigment, resin emulsion particles, an oxazoline group-containing compound, and an aqueous medium, and optionally other components such as additives. 【0086】 The ink of the present invention described above can be suitably used for printing on fabrics using an inkjet printer. By using the ink of the present invention in an inkjet printing method, articles can be obtained on fabrics with arbitrary images such as characters, patterns, and diagrams printed on them. Furthermore, due to the above-described configuration, the inkjet printing ink of the present invention exhibits excellent friction fastness of the printed image even at low heating temperatures during inkjet printing. Therefore, by using the inkjet printing ink of the present invention in inkjet printing on fabrics, energy can be saved in the drying process, and images with excellent friction fastness can be formed and printed (printed) even on fabrics containing materials with low heat resistance, such as polypropylene fibers and polyester fibers. 【0087】 2. Method for manufacturing printed materials on which images are printed on fabric. Printed materials (textiles) using the inkjet printing ink of the present invention can be manufactured by various methods, but among these manufacturing methods, a preferred method will be described. This manufacturing method is a method for manufacturing printed materials in which an image is printed on a fabric, comprising an image forming step of applying the inkjet printing ink of the present invention to a fabric using an inkjet printer to form an image. This manufacturing method will also be referred to as the manufacturing method for printed materials of the present invention. A transfer printing method using the inkjet printing ink of the present invention can also be employed. Conventional known methods can be used as the transfer printing method. Examples of transfer printing methods include a transfer paper manufacturing step of producing transfer paper with an image formed on it by ejecting the inkjet printing ink of the present invention onto a transfer paper substrate using an inkjet printer and drying it as necessary; a transfer step of transferring the image formed on the transfer paper to the fabric by placing the transfer paper produced in the transfer paper manufacturing step onto a fabric and heating and / or pressurizing it; and a peeling step of peeling the transfer paper from the fabric after the image has been transferred in the transfer step. 【0088】 In this specification, "textiles" encompass all textile products such as cloths and woven fabrics made from natural and / or synthetic fibers. Examples include woven fabrics, nonwoven fabrics, knitted fabrics, etc. The fibers constituting the textiles are not particularly limited and include, for example, natural fibers, chemical fibers, or mixtures thereof. 【0089】 Preferred natural fibers include, for example, silk, cotton, and wool. Chemical fibers include synthetic fibers, regenerated fibers, and semi-synthetic fibers. Preferred synthetic fibers include, for example, polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, polyethylene fibers, polypropylene fibers, and vinylon fibers. A preferred regenerated fiber is, for example, rayon. Preferred semi-synthetic fibers include acetate and triacetate. 【0090】 Among these, fabrics containing cotton, polyester fibers, and polypropylene fibers are preferred. As will be described later, the preferred heat treatment temperature differs depending on the type of fiber that makes up the fabric. Even for fabrics mainly composed of polyester fibers or polypropylene fibers, which have a low heat treatment temperature, the ink of the present invention makes it possible to produce printed materials with excellent friction fastness. Furthermore, even for fabrics like cotton, which were conventionally heat-treated at 160°C to fix the image and ensure fastness, the ink of the present invention makes it possible to produce printed materials with excellent friction fastness even at lower heating temperatures. 【0091】 The inkjet printer used in the image forming process and the transfer paper manufacturing process described above is not particularly limited, and any conventionally known inkjet printer can be used. The inkjet printer may be of any type, such as a piezo type, a thermal type, or a charge change control type (continuous ejection type), and a piezo type inkjet printer is particularly preferred. When using the above piezo type inkjet printer, the ink ejection conditions are not particularly limited. They can be appropriately selected depending on the properties of the ink of the present invention, the type of fabric, the type of image to be printed, etc. Furthermore, the viscosity of the inkjet printing ink of the present invention is preferably in the range of 2 to 20 mPa / s. The ink surface tension is preferably in the range of 25 to 45 mN / m. 【0092】 In the image forming process and the transfer paper manufacturing process described above, the ink of the present invention, ejected from the nozzle opening of the inkjet printer head, adheres to the surface of the fabric and the transfer paper substrate, respectively, to form an image. 【0093】 In the method for manufacturing printed materials of the present invention, it is preferable to include a step of heating the fabric on which the image has been formed in the image formation step at a temperature above room temperature (also referred to as a heat treatment step). Furthermore, in the transfer printing method, it is preferable to include a step of heating the fabric on which the image has been transferred from the transfer paper in the transfer step at a temperature above room temperature (also referred to as a heat treatment step). Heat treatment at a temperature above room temperature can promote the removal of volatile components such as aqueous media derived from the ink contained in the image formed on the fabric, thereby promoting the fixing of the image. In addition, the adhesion of the image can be improved by the film formation (fusion) of resin emulsion particles contained in the ink. Furthermore, the reaction to form the reaction product (C) described later also proceeds more easily. 【0094】 The heat treatment process may be performed simultaneously with the image formation or transfer process, or after it. A combination of both may also be used. For example, one method of performing the heat treatment process simultaneously with the image formation or transfer process is to heat the fabric while performing the image formation or transfer process. When the heat treatment process is performed after the image formation or transfer process, preferred heat treatment methods include heating using a heating and drying oven, heating using a heat press, heating using an infrared lamp, or using steam such as atmospheric pressure steam or high-pressure steam. Among these, it is preferable to perform the heat treatment process after the image formation or transfer process, as simultaneous heating may disrupt the airflow. 【0095】 The heating temperature in the above heat treatment step is preferably 90 to 180°C. The upper limit is more preferably 150°C or lower, even more preferably 130°C or lower, and particularly preferably 120°C or lower. The lower limit is more preferably 95°C or higher, and even more preferably 100°C or higher. In the heat treatment step, the recommended heating temperature and time differ depending on the fibers that make up the fabric. For example, cotton is 160°C, polypropylene is 125°C, and polyester is 110°C, all for 5 minutes or less, preferably 3 minutes or less, and more preferably 2 minutes or less. The printed material (printed material with an image formed on the fabric) obtained after the above heat treatment step may be washed with water and dried. Using the inkjet printing ink of the present invention, the method for manufacturing printed materials of the present invention, and the transfer printing method described above, it is possible to produce printed materials (printed materials in which an image is formed on fabric) with excellent friction fastness of the printed image, even at low heating temperatures, in an energy-saving and environmentally friendly manner. To obtain a printed material with excellent friction fastness in a short time, it is preferable that the heating temperature be 90°C or higher, as described above. However, the heating temperature in the above heat treatment step is not limited to the above range, and may be, for example, a temperature near room temperature, such as 15-25°C. Even at such temperatures, the friction fastness of the printed image can be improved by heating for a long time. From the viewpoint of shortening the heating time, 30°C or higher is preferable, 50°C or higher is more preferable, and 90°C or higher is even preferable. Here, "room temperature" refers to, for example, 15-25°C, while "room temperature" refers to the actual temperature inside a room, which is usually considered to be around 15-25°C. In this specification, printing means an image forming step in which inkjet printing ink is applied to a fabric using an inkjet printer to form an image. The printing method of the present invention using the inkjet printing ink of the present invention, and the image printed by the above transfer printing method, etc., may or may not be subjected to heat treatment at a temperature above room temperature. 【0096】 3. Image-printed articles and image-fixed articles The present invention further provides an image-printed article. The image-printed article provided by the present invention is an image-printed article in which an image made of the inkjet printing ink of the present invention is printed on part or all of a fabric, and comprises a pigment and a resin, wherein the resin comprises a reaction product (C) of an acrylic-styrene polymer (A) having a carboxyl group and an oxazoline group-containing compound (B). In the above printed image, it is preferable that the pigment is dispersed in the resin with the resin as a binder. Furthermore, it is preferable that the above inkjet printing ink contains an acrylic-styrene polymer (A) having a carboxyl group. The above reaction product (C) is formed even without heating to temperatures above room temperature, and is also formed during room temperature drying. The reaction proceeds faster at higher temperatures. Although the rate of formation of the above reaction product (C) is faster when heated to temperatures above room temperature, it is thought that small amounts are also formed over time even during room temperature drying. 【0097】 The present invention further provides an image-fixed article. The image-fixed article provided by the present invention is an image-fixed article in which an image containing a pigment and a resin is fixed to part or all of a fabric, characterized in that the resin contains a reaction product (C) of an acrylic-styrene polymer having a carboxyl group (A) and an oxazoline group-containing compound (B). The fixed image contains a pigment and a resin. In the fixed image, it is preferable that the pigment is dispersed and contained with the resin as a binder. Here, "an image containing pigment and resin is fixed to part or all of the fabric" preferably means that the image containing pigment and resin is attached in a manner that provides excellent friction fastness. 【0098】 <Resin> The above resin contains a reaction product (C) of an acrylic-styrene polymer (A) having a carboxyl group and an oxazoline group-containing compound (B). The acrylic-styrene polymer (A) having a carboxyl group will be described below. The acrylic-styrene polymer (A) having a carboxyl group is also referred to as polymer (A). 【0099】 The monomers used to form the above polymer (A) (styrene monomers, (meth)acrylic monomers, etc.) are similar to the monomers used to form the carboxyl-styrene polymer, which is a preferred form of resin constituting the resin emulsion particles constituting the ink of the present invention. Specific examples are omitted. 【0100】 The acrylic-styrene polymer in polymer (A) described above is a copolymer of an acrylic monomer and a styrene monomer. Polymer (A) only needs to contain constituent units derived from (meth)acrylic monomers and constituent units derived from styrene monomers, and may also contain other constituent units. However, the total content of constituent units derived from (meth)acrylic monomers and styrene monomers relative to 100% by mass of the total constituent units of polymer (A) is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100 mol%. 【0101】 The content of styrene monomer-derived structural units in the polymer (A) described above is not particularly limited, but is preferably 1 to 55% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 45% by mass, based on 100% by mass of the total amount of structural units derived from (meth)acrylic monomers and styrene monomers. By setting the styrene monomer content within the above range, it is easier to obtain image-printed articles and image-fixed articles (e.g., printed materials) that have superior texture or wash fastness. 【0102】 The carboxyl group content in polymer (A) is preferably 0.06 to 3% by mass per 100% by mass of polymer (A). Furthermore, it is preferable that the carboxyl group is a carboxyl group derived from (meth)acrylic acid. Therefore, it is more preferable that polymer (A) contains constituent units derived from (meth)acrylic acid. The content of constituent units derived from (meth)acrylic acid in polymer (A) is preferably 0.1 to 5% by mass, more preferably 0.2 to 4% by mass, and even more preferably 1 to 3% by mass, per 100% by mass of the total amount of constituent units derived from (meth)acrylic monomers and styrene monomers. 【0103】 The polymer (A) described above preferably further contains structural units derived from (meth)acrylic acid esters. In particular, it is preferable that it contains structural units derived from alkyl (meth)acrylates and structural units derived from hydroxyalkyl (meth)acrylates. Furthermore, it is even more preferable that it contains structural units derived from alkyl (meth)acrylates and structural units derived from hydroxyalkyl (meth)acrylates. 【0104】 In the above-mentioned alkyl (meth)acrylate-derived structural unit, it is preferable that the alkyl group contained in the structural unit includes an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms. Furthermore, it is also preferable that the alkyl group includes two or more alkyl groups with different numbers of carbon atoms. For example, this includes a form containing an alkyl group having 1 to 5 carbon atoms and an alkyl group having 6 to 18 carbon atoms, a form containing an alkyl group having 1 carbon atom and an alkyl group having 8 to 18 carbon atoms, a form containing an alkyl group having 1 carbon atom, an alkyl group having 4 to 6 carbon atoms and an alkyl group having 8 to 18 carbon atoms, and a form containing an alkyl group having 2 to 6 carbon atoms and an alkyl group having 8 to 12 carbon atoms. In addition, in the above-mentioned hydroxyalkyl (meth)acrylate-derived structural unit, it is preferable that the hydroxyalkyl group has 1 to 18 carbon atoms, and more preferably 2 to 4 carbon atoms. 【0105】 Furthermore, the polymer (A) may include structural units other than those derived from (meth)acrylic monomers and styrene monomers. Examples of other structural units include those derived from monomers such as acrylonitrile, vinyl acetate, and acrylamide. 【0106】 The oxazoline group-containing compound (B) will now be described. The oxazoline group-containing compound (B) is the same as the oxazoline group-containing compound contained in the ink of the present invention, including its preferred form, and the above description can be applied mutatis mutandis. Therefore, the description will be omitted. 【0107】 The reaction product (C) of polymer (A) and oxazoline group-containing compound (B) will be described. The above reaction product (C) is produced by the reaction of a carboxyl group of polymer (A) and an oxazoline group of oxazoline group-containing compound (B). Preferably, this reaction forms an amide ester bond. The content of the amide ester bond is not particularly limited, but is 0.05 to 5% by mass per 100% by mass of the resin. More preferably, it is 0.1 to 3% by mass. The content of the above reaction product (C) in the above resin is not particularly limited, but is preferably 0.1 to 50% by mass per 100% by mass of the resin. More preferably, it is 0.2 to 40% by mass, and even more preferably, 0.3 to 30% by mass. 【0108】 The above resin preferably further contains polymer (A) in addition to the above reaction product (C). The inclusion of polymer (A) makes it easier to produce a fabric with a superior texture. The content of polymer (A) in the above resin is preferably 50 to 99.9% by mass relative to 100% by mass of the resin. The lower limit is more preferably 60% by mass or more, even more preferably 70% by mass or more, and the upper limit is more preferably 99.8% by mass or less, even more preferably 99.7% by mass, and even more preferably 99% by mass or less. 【0109】 The above resin may further contain an oxazoline group-containing compound (B). The content of the polymer (B) in the above resin is preferably 0 to 5% by mass, based on 100% by mass of the resin. More preferably, it is 0 to 2% by mass, and even more preferably 0 to 1% by mass. 【0110】 <Pigments> The above-mentioned pigments are the same as those constituting the ink of the present invention, including their preferred forms, and the above description can be applied mutatis mutandis. Therefore, the description is omitted. 【0111】 <Printed image and fixed image> The above printed image and fixed image include the above resin and the above pigment. The total content of resin and pigment in the above printed image and fixed image is preferably 80 to 100% by mass relative to 100% by mass of the image. More preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass or more. The resin content in the above printed image and fixed image is preferably 20 to 95% by mass, relative to 100% by mass of the image. More preferably, it is 25 to 90% by mass, and even more preferably 30 to 85% by mass. 【0112】 The above printed image only needs to be printed on part or all of the fabric. The above image of the attached material only needs to show that it is attached to part or all of the fabric. The film thickness of the printed image and the fixed image described above is not particularly limited, but is preferably 0.1 to 1000 μm, more preferably 0.3 to 500 μm, and even more preferably 0.5 to 100 μm. The above film thickness can be determined by observing and measuring the value using, for example, a laser microscope. 【0113】 <Fabric> The definition of fabric in the image-printed articles and image-fixed articles of the present invention, and the specific materials that can be used, are the same as those described in "Method for Manufacturing Image-Printed Fabric" and can be applied mutatis mutandis. The preferred forms are also the same. That is, fabrics containing cotton, polyester fibers, and polypropylene fibers are preferred, and fabrics containing cotton as the main component, fabrics containing polyester fibers as the main component, and fabrics containing polypropylene fibers as the main component are more preferred. 【0114】 The image-printed articles and image-fixed articles of the present invention have been described above. The image-printed articles of the present invention exhibit excellent frictional fastness even when the temperature during the heat treatment process in printing is low. A preferred embodiment of the heat treatment process is the same as that described in the section on the manufacturing method of the printed article of the present invention. Furthermore, the image-fixed articles of the present invention exhibit excellent frictional resistance. Here, "excellent friction fastness" preferably means that, in accordance with the method specified in JIS L0849, a dry friction test and a wet friction test are performed using a Type II testing machine with attached white cloth made of cotton No. 3-1, under a load of 200g and 100 back-and-forth movements, and evaluated using a grayscale of discoloration, both the dry friction test and the wet friction test receive a rating of 3-4 or higher. 【0115】 The image-printed articles and image-fixed articles of the present invention can be manufactured, for example, using an ink particularly preferred form among the inkjet printing inks of the present invention. In this case, it is preferable to employ the method for manufacturing fabric printed with the image of the present invention, or the method for manufacturing fabric printed with the image according to the transfer printing method described above. [Examples] 【0116】 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "percent mass". The measurement and evaluation methods are as follows: 【0117】 <Average particle size of resin emulsion particles> The average particle size of the resin emulsion particles was determined using the cumulant method obtained when the resin emulsion was measured using a particle size distribution analyzer (manufactured by Otsuka Electronics Co., Ltd., model number: FPAR-1000) that employs dynamic light scattering. 【0118】 <Average particle size of pigments> The average particle size of the pigment was determined using the cumulant method obtained by measuring the pigment dispersion using a particle size distribution analyzer (manufactured by Otsuka Electronics Co., Ltd., model number: FPAR-1000) based on dynamic light scattering. 【0119】 <Ink viscosity> Each ink obtained in each example and comparative example was measured using an E-type viscometer, TPE-100 (manufactured by Toki Sangyo), at a rotor R24, 0.8 degrees Celsius, and 25°C. 【0120】 <Ink storage stability> Each ink obtained in each example and comparative example was sealed in a sealed container and stored in a constant temperature bath at 50°C for 30 days, and then evaluated according to the evaluation criteria below. ◎: Viscosity change rate before and after storage is less than 5%. ○: Viscosity change rate before and after storage is 5-10%. △: Viscosity change rate before and after storage: 11-20%. ×: Gelifies upon storage. 【0121】 <Discharge stability> Each ink obtained in the examples and comparative examples was introduced into a Mastermind MMP-TX13 textile printer, and nozzle check printing (printing ruled lines by sequentially ejecting ink from all 180 nozzles) was performed on PET film. Splashing (bending) and dot defects were visually evaluated. Furthermore, after capping the print head and letting it stand for one week, nozzle check printing was performed again and splashing (bending) and dot defects were visually evaluated. Inks that were marked with a △ or × had insufficient ejection stability. ◎: There are absolutely no scattered (bent) or dead pixels, neither initially nor after one week. ○: There are 1 to 2 more scattered (bent) or dead pixels initially and 1 week later. △: There are 3 to 4 more scattered (bent) or dead pixels initially and 1 week later. ×: There are 5 or more scattered (bent) or dead pixels, with the highest number occurring initially and after one week. 【0122】 <Abrasion resistance> The fabrics printed with each image obtained in each example and comparative example were subjected to dry and wet friction tests using a Type II testing machine with attached white cotton fabric (No. 3-1) under a load of 200g for 100 cycles, according to the method specified in JIS L0849, and evaluated using a grayscale of color change. For Example 7, which uses white ink, the evaluation was performed on a cotton fabric (100% cotton black T-shirt manufactured by Hanes). The fabrics printed with images marked with △ and × showed insufficient friction fastness. ◎: Both dry friction test and wet friction test are grade 4-5 or higher. ○: Both the dry friction test and the wet friction test were graded 3-4 to 4. △: Both dry friction test and wet friction test results are grade 2-3 to 3. ×: Either the dry friction test or the wet friction test results are 2nd grade or lower. 【0123】 <Washfastness> The fabrics printed with the images obtained in each example and comparative example were subjected to 10 washes in a household washing machine using normal washing conditions (washing mode: wash → rinse → spin → dry, using Ariel liquid detergent (manufactured by P&G)), and the degree of fading was evaluated using a color change grayscale. ◎: 4-5 grade ~ 5 grade. 〇: 3-4 grade ~ 4 grade. △: 2-3 grade ~ 3 grade. ×: Level 2 or lower. 【0124】 <Texture> The fabrics printed with the images obtained in each example and comparative example were evaluated by touch. ◎: Fabric with an image printed on it that folds easily and is close to the softness of the fabric itself. ○: Fabric with a printed image that folds easily, but feels slightly stiffer than the fabric itself. △: Fabric with a printed image that feels stiff or rough. ×: Fabric with an image printed on it that is too stiff to bend freely. 【0125】 <Example of emulsion manufacturing> [Emulsion Manufacturing Example 1] 252 parts of deionized water were placed in a flask equipped with a dropping funnel, stirrer, nitrogen gas inlet tube, thermometer, and reflux condenser. A dropwise pre-emulsion was prepared in the dropping funnel, consisting of 437 parts of deionized water, 80 parts of a 25% aqueous solution of emulsifier (ADEKA Corporation, product name: Adekaryasorb SR-10), 25 parts of acrylic acid, 565 parts of 2-ethylhexyl acrylate, 50 parts of cyclohexyl methacrylate, 10 parts of hydroxyethyl methacrylate, and 350 parts of styrene. 44 parts of this pre-emulsion, representing 3% of the total amount of monomer components, were added to the flask. The mixture was heated to 80°C while slowly blowing in nitrogen gas, and 30 parts of a 5% aqueous solution of ammonium persulfate were added to initiate polymerization. Subsequently, the remaining portion of the dropwise pre-emulsion and 30 parts of the 5% aqueous solution of ammonium persulfate were uniformly added dropwise to the flask over a period of 240 minutes. After the dropwise addition was complete, the contents of the flask were maintained at 80°C for 180 minutes, and the pH was adjusted to 8.5 and the solids content to 50% by adding 25% aqueous ammonia and deionized water to complete the polymerization. After the resulting reaction solution was cooled to room temperature, the emulsion was obtained by filtering it through a 300-mesh wire mesh. The styrene monomer content in the emulsion resin particles was 35%, the Tg was -21°C, and the average particle size of this emulsion was 200 nm. 【0126】 [Emulsion Manufacturing Example 2] An emulsion was obtained in the same manner as in Emulsion Preparation Example 1, except that 7 parts of the dropwise pre-emulsion, representing 0.5% of the total amount of monomer components, were added to the flask. The styrene monomer content of this emulsion resin particles was 35%, the Tg was -21°C, and the average particle size of this emulsion was 310 nm. 【0127】 [Emulsion Manufacturing Example 3] An emulsion was obtained in the same manner as in Emulsion Preparation Example 1, except that 87 parts of the dropwise pre-emulsion, representing 6% of the total amount of monomer components, were added to the flask. The styrene monomer content of this emulsion resin particles was 35%, the Tg was -21°C, and the average particle size of this emulsion was 140 nm. 【0128】 [Emulsion Manufacturing Example 4] An emulsion was obtained in the same manner as in Emulsion Preparation Example 1, except that the styrene in the dropper pre-emulsion was changed to 50 parts and 300 parts of methyl methacrylate were newly added. The styrene monomer content in the emulsion resin particles was 5%, the Tg was -20°C, and the average particle size of this emulsion was 200 nm. 【0129】 [Emulsion Manufacturing Example 5] An emulsion was obtained in the same manner as in Emulsion Preparation Example 1, except that the cyclohexyl methacrylate in the dropper pre-emulsion was changed to 0 parts and the styrene was changed to 200 parts. The styrene monomer content in this emulsion resin particles was 20%, the Tg was -22°C, and the average particle size of this emulsion was 210 nm. 【0130】 [Emulsion Manufacturing Example 6] An emulsion was obtained in the same manner as in Emulsion Preparation Example 1, except that the amount of 2-ethylhexyl acrylate in the dropper pre-emulsion was changed to 465 parts, the amount of cyclohexyl methacrylate was changed to 0 parts, and the amount of styrene was changed to 500 parts. The styrene monomer content in this emulsion resin particles was 50%, the Tg was -5°C, and the average particle size of this emulsion was 200 nm. 【0131】 <Examples of Pigment Dispersion Manufacturing> [Pigment dispersion manufacturing example 1] Three parts of the dispersant Joncryl 678 (BASF), 1.3 parts of dimethylaminoethanol, and 81 parts of deionized water were stirred and mixed at 70°C. Next, 15 parts of the blue pigment CIPigment Blue 15:3 LIONOL BLUE FG-7330 (Toyo Ink), 0.1 parts of the surfactant Orfin D-10PG (Nisshin Chemical Industry), and 0.5 mm zirconia beads were packed into the mixture to a volume of 50%. The mixture was dispersed using a bead mill and filtered through a 1 μm pore size filter (Advantec, MCP-1-C10S) to obtain a blue pigment dispersion containing 15% pigment. The average particle size was 90 nm. 【0132】 [Pigment dispersion manufacturing example 2] A blue pigment dispersion containing 15% pigment was obtained in the same manner as in Pigment Dispersion Production Example 1, except that the blue pigment was changed to metal-free CIPigment Blue16 (manufactured by Tokyo Chemical Industry Co., Ltd.). The average particle size was 95 nm. 【0133】 [Pigment dispersion manufacturing example 3] Five parts of the dispersant Discoat N-14 (manufactured by Daiichi Kogyo Seiyaku), six parts of propylene glycol, seventy parts of deionized water, and 100 parts of titanium dioxide CR-95 (manufactured by Ishihara Sangyo) were packed into a mixture containing 0.5 mm particle size zirconia beads at a volume ratio of 50%. The mixture was dispersed using a bead mill to obtain a white pigment dispersion with a pigment content of 55%. The average particle size was 330 nm. 【0134】 <Examples> [Example 1] (Ink manufacturing) Ink (1) was produced by mixing 30 parts of the emulsion from Emulsion Production Example 1 (15 parts as emulsion particles), 23 parts of the pigment dispersion from Pigment Dispersion Production Example 1 (15 parts as pigment), 1.2 parts of Epocross WS-700 (manufactured by Nippon Shokubai, 25% solids content) (0.3 parts as solids), 2 parts of diethylene glycol monobutyl ether, 15 parts of triethylene glycol, 0.3 parts of the surfactant KF-6011 (manufactured by Shin-Etsu Chemical), and 28.5 parts of deionized water, and filtering the mixture through a 1 μm pore size filter (manufactured by Advantec, MCP-1-C10S). (Image formation by inkjet method) The ink (1) obtained above was introduced into an inkjet printer: Mastermind Textile Printer MMP-TX13, and a solid print of 120mm x 120mm was performed on a cotton fabric (Hanes 100% cotton white T-shirt) using blue ink at 1440dpi x 1440dpi, print speed setting 8, to form an image on the fabric. The fabric with the image formed on it was then heat-treated in a 110°C hot air dryer for 90 seconds to obtain the fabric with the printed image (1). 【0135】 [Examples 2-13 and Comparative Examples 1-8] Ink (2) to (13) for Examples 2 to 13 and ink (c1) to (c8) for Comparative Examples 1 to 8 were manufactured in the same manner as in Example 1, except that the type and amount of each raw material used in Example 1 were changed as shown in Tables 1 to 3, and the amount of deionized water used was adjusted so that the total amount was 100 parts. For the oxazoline group-containing compound listed in Tables 1 to 3, Epocross WS-700 (manufactured by Nippon Shokubai, solid content 25%) was used; for the carbodiimide group-containing compound, Carbodilite SV-02 (manufactured by Nisshinbo Chemical, solid content 40%) was used; and for the blocked isocyanate compound, Bahijule BL2867 (manufactured by Sumika Covestro Urethane, solid content 38%) was used. 【0136】 Next, using the respective inks for each example and comparative example, images were formed by inkjet printing in the same manner as in Example 1, obtaining fabrics (2) to (13) and fabrics (c1) to (c8) on which each image was formed. The types of fabrics and heat treatment conditions used in each example and comparative example are shown in Tables 1 to 3. For the polyester fabric, Gunze's 100% polyester white T-shirt was used, and for the polypropylene fabric, a fabric made of 100% polypropylene fibers was used. Fabrics (2) to (13) and fabrics (c1) to (c8) were each obtained by forming images using the inkjet method in the same manner as in Example 1, and then by heat treatment under the heat treatment conditions shown in Tables 1 to 3, in the same manner as in Example 1, and are fabrics with printed images. 【0137】 Tables 1-3 show the evaluation results for the inks, inkjet characteristics, and printed images produced in each example and comparative example. 【0138】 [Table 1] 【0139】 [Table 2] 【0140】 [Table 3] 【0141】 As shown in Tables 1-2, the inks (1) to (13) obtained in Examples 1-13 all exhibited excellent ejection stability, and the fabrics (1) to (13) on which images were printed using each ink with an inkjet printer all showed excellent friction fastness of the printed images, even when the heat treatment conditions were 110°C for 90 seconds or 110°C for 60 seconds. Furthermore, the fabrics (1) to (13) obtained in Examples 1 to 13 exhibited excellent friction fastness, and the printed images were firmly fixed to the fabric.

Claims

[Claim 1] An inkjet printing ink comprising resin emulsion particles, an oxazoline group-containing compound, and an aqueous medium, The resin emulsion particles mainly consist of an acrylic-styrene polymer having a carboxyl group, The average particle size of the resin emulsion particles is 150 nm or more, and the content of the resin emulsion particles is 10 to 20% by mass relative to 100% by mass of the inkjet printing ink. The content of the oxazoline group-containing compound is 0.5 to 10% by mass relative to 100% by mass of the resin emulsion particles. An inkjet printing ink characterized by the following features. [Claim 2] The content of the carboxyl group is 0.06 to 3% by mass with respect to 100% by mass of the resin emulsion particles. The inkjet printing ink according to claim 1. [Claim 3] The acid value of the resin emulsion particles is 0.5 to 50 mg KOH / g. The inkjet printing ink according to claim 1 or 2. [Claim 4] The content of styrene monomers in the monomer for forming the acrylic-styrene polymer is 1 to 55% by mass with respect to 100% by mass of the total amount of (meth)acrylic monomers and styrene monomers. The inkjet printing ink according to claim 1 or 2. [Claim 5] The acrylic-styrene polymer is produced by emulsion polymerization in the presence of a reactive emulsifier. The inkjet printing ink according to claim 1 or 2. [Claim 6] The oxazoline group-containing compound comprises a water-soluble oxazoline group-containing polymer. The inkjet printing ink according to claim 1 or 2. [Claim 7] The aqueous medium comprises water and an organic solvent, The organic solvent is preferably propylene glycol, glycerin, diethylene glycol, triethylene glycol, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monobutyl ether, polyethylene glycol (moles of EO added = 2 to 4) monobutyl ether, and 2-pyrrolidone, and more preferably comprises at least one selected from the group consisting of propylene glycol, triethylene glycol, polyethylene glycol (moles of EO added = 2 to 4) monobutyl ether, and 2-pyrrolidone. The inkjet printing ink according to claim 1 or 2. [Claim 8] A method for manufacturing a printed material having an image printed on a fabric, comprising an image forming step of applying an inkjet printing ink according to claim 1 or 2 to a fabric using an inkjet printer to form an image. [Claim 9] An image-printed article having a printed image made of inkjet printing ink according to claim 1 or 2 printed on part or all of a piece of fabric, wherein the image-printed article comprises a resin, the resin comprising a reaction product (C) of an acrylic-styrene polymer having a carboxyl group (A) and an oxazoline group-containing compound (B).

Images