Ink for inkjet textile printing, method of manufacturing a print using the ink, and article having an adhered image

Abstract

The ink for inkjet textile printing of the present invention contains a pigment, resin emulsion particles, an oxazoline group-containing compound, and an aqueous medium, wherein the average particle diameter of the resin emulsion particles is 150 nm or more, the content of the resin emulsion particles is 10 to 20 mass% with respect to 100 mass% of the ink for inkjet textile printing, and the content of the oxazoline group-containing compound is 0.5 to 10 mass% with respect to 100 mass% of the resin emulsion particles.

Description

Technical Field

[0001] This invention relates to inks for inkjet textile printing, methods for manufacturing printed materials using said inks, and articles having an adhered image. Background Technology

[0002] Currently, textile printing methods using inkjet printing with inks containing pigments as colorants (methods for obtaining printed textiles by inkjet printing) are attracting attention. Ink used for inkjet printing needs to possess properties specific to inkjet printing, such as dispersion stability, jetting stability, and fixing properties to the medium. In addition to these properties, inkjet textile printing inks used in textile printing methods by inkjet printing also need to possess properties such as print image fastness, for example, rubbing fastness and wash fastness, and texture. In these cases, for example, inks containing crosslinking agents have been proposed to provide textile printing inks with excellent fastness, etc. (e.g., Patent Documents 1 and 2). Patent Documents 1 and 2 provide examples showing that printed textiles obtained by applying the corresponding textile printing inks by inkjet printing to fabrics made of 100% cotton (in Patent Document 1) or cotton fabrics coated with a pretreatment liquid (in Patent Document 2) exhibit excellent fastness, such as rubbing fastness. In each document, a heat treatment at 160°C is performed after inkjet printing.

[0003] In Patent Document 1, an aqueous resin dispersion (resin emulsion) and an oxazoline compound as a crosslinking agent (2) were used in Comparative Example 7. However, the content of resin emulsion particles (the content of solid components in the resin emulsion) was 2.6% by mass relative to 100% by mass of the ink for inkjet textile printing, which was much lower than 10% by mass, and the content of the oxazoline-containing compound was 88% by mass relative to 100% by mass of the resin emulsion particles, which was much higher than 10% by mass. Patent Document 1 does not mention or suggest the feature of providing an inkjet textile printing ink that, when used for inkjet textile printing, not only provides a printed image with excellent rubbing fastness even when inkjet textile printing is performed at low heating temperatures, but also has excellent jetting stability.

[0004] Patent Document 2 also does not mention or suggest features such as providing ink for inkjet textile printing that, when used in inkjet textile printing, not only provides printed images with excellent rub fastness even when inkjet printing is performed at low heating temperatures, but also has excellent jetting stability. Furthermore, Patent Document 2 does not mention any compounds containing an oxazoline group.

[0005] Citation List

[0006] Patent documents

[0007] Patent Document 1: JP2009-215506A

[0008] Patent Document 2: JP2011-105805A Summary of the Invention

[0009] Technical issues

[0010] In inkjet textile printing, heat treatment is preferably performed during or after image formation via inkjet printing to fix the image; however, the permissible temperature varies depending on the fabric material. For cotton, heat treatment can even be performed at 160°C. However, for many fabrics (e.g., fabrics made of polyester fibers), the permissible temperature is lower. Therefore, it is desirable to develop an ink for textile printing that exhibits excellent image fastness and other properties even at relatively low temperatures. Furthermore, from the perspective of print image reproducibility, excellent jetting stability of the ink is crucial in inkjet textile printing during printing.

[0011] One object of the present invention is to provide an ink for inkjet textile printing that, when used in inkjet textile printing, not only provides a printed image with excellent rub fastness even when inkjet textile printing is performed at low heating temperatures, but also has excellent jetting stability.

[0012] Solution to the problem

[0013] The inventors focused on the aforementioned problems and conducted detailed research on inkjet textile printing inks for fabric printing. As a result, the inventors discovered that by adjusting the particle size and content of the resin emulsion particles to values ​​within a specific range and by incorporating specific amounts of a specific compound, inks containing pigments, resin emulsion particles, and an aqueous medium can provide printed images with excellent rubbing fastness even when applied to inkjet textile printing using low heating temperatures, and also exhibit excellent jetting stability during printing. This completes the present invention.

[0014] Specifically, the inkjet textile printing ink of the present invention is an inkjet textile printing ink comprising pigment, resin emulsion particles, an oxazoline-containing compound, and an aqueous medium, characterized in that 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 textile printing ink, and the content of the oxazoline-containing compound is 0.5% to 10% by mass relative to 100% by mass of the resin emulsion particles.

[0015] Beneficial effects of the invention

[0016] Due to the above configuration, the inkjet textile printing ink of the present invention exhibits excellent jetting stability during printing, and provides printed images with excellent rubbing fastness even when inkjet printing is performed at low heating temperatures. Therefore, by using the inkjet textile printing ink of the present invention in inkjet printing on fabrics and the like, not only can energy savings be achieved in the drying step, but printing (textile printing) including steps for forming images with excellent rubbing fastness can also be stably performed even on fabrics containing polyester fibers or other materials with low heat resistance temperatures. Detailed Implementation

[0017] The present invention will now be described in detail.

[0018] Any combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0019] In this specification, the term "(meth)acrylate" means "acrylate" or "methacrylate", and the term "of (meth)acrylic" means "of acrylic acid" or "of methacrylic acid". There are instances where (meth)acrylate is referred to as (meth)acrylic acidester.

[0020] In this specification, the phrase "heating temperature during inkjet printing" refers to the heating temperature during or after image formation using an inkjet apparatus (inkjet printer) in textile printing methods. However, when an image is formed using an inkjet apparatus while the fabric is being heated (i.e., heat treatment is performed during image formation, but no heating is performed after image formation), this phrase refers to the temperature used for heating during image formation. When an image is formed using an inkjet apparatus while the fabric is being heated and heating is performed after image formation, this phrase refers to the higher of the two temperatures: the temperature used for heating during image formation and the temperature used for heating after image formation.

[0021] 1. Ink for inkjet textile printing

[0022] The inkjet textile printing ink of the present invention comprises pigment, resin emulsion particles, an oxazoline-containing compound, and an aqueous medium, and is characterized in that 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 textile printing ink, and the content of the oxazoline-containing compound is 0.5% to 10% by mass relative to 100% by mass of the resin emulsion particles.

[0023] The inkjet textile printing ink of the present invention is also referred to as the ink of the present invention. In addition to the components mentioned above, the ink of the present invention may, as needed, contain any of the other components described below. The components constituting the ink of the present invention are described below.

[0024] Pigments

[0025] The ink of this invention contains pigments. Examples of pigments include organic and inorganic pigments, and one of these pigments can be used alone or in combination of two or more. Any of the pigments can be used in combination with extender pigments as needed.

[0026] Examples of organic pigments include: azo pigments such as benzidine and Hansa Yellow; diazo pigments; azomethyl pigments; methine pigments; anthraquinone pigments; phthalocyanine pigments such as phthalocyanine Blue; perinone pigments; perylene pigments; diketopyrrole pigments; thioindole pigments; iminoisoindoline pigments; isoindolineone pigments such as iminoisoindolineone; dioxazine pigments; quinacridone pigments such as quinacridone Red and quinacridone Violet; flavanone pigments; indanone pigments; anthrapyrimidine pigments; carbazole pigments; monoarylide yellow; diarylide yellow; and benzoimidazolone yellow. Yellow), Tolyl Orange, Naphthol Orange, and quinophthalone pigments.

[0027] There are no particular restrictions on hue, and any of the colored pigments such as yellow, magenta, cyan, blue, red, orange, and green can be used. Specific examples include CI-named products such as Pigment Yellow, Pigment Red, Pigment Orange, Pigment Violet, Pigment Blue, and Pigment Green. When the ink is to be applied to polypropylene fabrics, it is preferable to use metal-free organic pigments from the viewpoint of not promoting the pyrolysis of polypropylene. Specifically, Pigment Blue 16, etc., can be selected.

[0028] Examples of inorganic pigments include: titanium dioxide, antimony trioxide, zinc oxide such as zinc white, zinc barium white, lead white, iron oxide red, iron oxide black, chromium oxide green, carbon black, chrome yellow, molybdenum red, ferrous ferrocyanide (Prussian Blue), ultramarine, and lead chromate. Examples of inorganic pigments also include: pigments with flattened shapes, such as mica, clay, aluminum powder, talc, and aluminum silicate; and extender pigments, such as calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, and magnesium carbonate. Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black.

[0029] Among such inorganic pigments, preferred white pigments include titanium dioxide, antimony trioxide, zinc oxide such as zinc white, zinc barium white, lead white, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, magnesium carbonate, clay, talc, and aluminum silicate. Of these, titanium dioxide is preferred from the perspective of high refractive index and excellent hiding power. Titanium dioxide with a rutile crystal structure is particularly preferred.

[0030] Preferred coloring pigments include the aforementioned organic pigments, iron oxide red, iron oxide black, chromium oxide green, carbon black, lead yellow, molybdenum red, ferrous ferrocyanide (Prussian blue), ultramarine, lead chromate, etc.

[0031] From the perspective of dispersion stability and coloring performance or hiding power, the average particle size of the pigment is ideally 10 to 1,000 nm, preferably 20 to 500 nm.

[0032] In the case of white pigments, from the perspective of excellent hiding performance, the average particle size is preferably 100 to 500 nm; the lower limit is more preferably 150 nm or more, still more preferably 200 nm or more, and the upper limit is more preferably 450 nm or less, still more preferably 400 nm or less.

[0033] In the case of coloring pigments, especially from the perspective of coloring performance, the average particle size is preferably 20 to 200 nm; the lower limit is more preferably 40 nm or more, still more preferably 50 nm or more, and the upper limit is more preferably 150 nm or less, still more preferably 100 nm or less.

[0034] The average particle size of the pigment is the average particle size in the ink of this invention. The average particle size of the pigment can be determined using a laser diffraction / scattering type particle size distribution analyzer or by dynamic light scattering. For example, it can be detected using a particle size distribution analyzer based on dynamic light scattering (product number: FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.), and the value obtained therefrom by the cumulative method can be used. However, in cases where it is difficult to detect by dynamic light scattering (e.g., for black pigments), it can be detected using a laser diffraction / scattering type particle size distribution analyzer, and the 50% particle size determined by the resulting volume-based particle size distribution can be used as the average particle size.

[0035] The pigments in the ink of the present invention are preferably in a state that has been dispersed and stabilized using a dispersant. Examples of dispersants include: poly((meth)acrylate), such as poly((meth)acrylate) and poly((meth)acrylate salt); copolymers of (meth)acrylate with one or more monomers containing olefinic unsaturated double bonds (such as (meth)acrylate, (meth)acrylonitrile, (meth)acrylamide, styrene, maleic acid, calcium maleate, maleate ester and vinyl acetate); poly(vinyl alcohol); and polyvinylpyrrolidone.

[0036] <Resin Emulsion Particles>

[0037] The resin emulsion particles contained in the ink of the present invention are described.

[0038] Although there are no particular restrictions on the resin emulsion particles, the resin emulsion particles are preferably resin particles derived from aqueous emulsions.

[0039] There are no particular restrictions on the shape of the resin emulsion particles, but they are usually spherical. The shape can be determined using transmission electron microscopy or scanning electron microscopy.

[0040] The average particle size of the resin emulsion particles is 150 nm or more. Because the average particle size is 150 nm or more, it is easy to incorporate a high concentration of resin emulsion particles while maintaining the ink viscosity within an appropriate range. An average particle size of 180 nm or more is more preferred, still more preferred to be greater than 200 nm, and even more preferred to be 210 nm or more. On the other hand, while there is no particular upper limit, an average particle size of 350 nm or less is preferred, more preferred to be 330 nm or less, and even more preferred to be 300 nm or less.

[0041] In this specification, the average particle size of the resin emulsion particles is a value obtained by detection using a particle size distribution analyzer based on dynamic light scattering (product number: FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.) and the cumulative method.

[0042] There are no particular limitations on the glass transition temperature of the resin emulsion particles. However, from the viewpoint that printed textiles obtained using the ink of the present invention easily have excellent texture, the glass transition temperature is preferably below 0°C. More preferably, it is below -10°C, and still more preferably below -15°C. On the other hand, although there is no particular lower limit, the glass transition temperature is preferably above -50°C, and more preferably above -40°C.

[0043] The values ​​of the glass transition temperature can be obtained by any of differential scanning calorimetry (DSC), differential thermal analysis (DTA), and thermomechanical analysis (TMA). However, values ​​obtained by differential scanning calorimetry (DSC) are preferred. Unless otherwise specified, the glass transition temperatures in this specification are values ​​obtained by differential scanning calorimetry (DSC).

[0044] However, in cases where the glass transition temperature can be determined by calculation using the Fox equation based on the composition of the resin components in the resin emulsion particles, as described later, such as in the cases of vinyl resins, (meth)acrylic resins, acrylic / styrene polymers, etc., the calculated value can be used instead.

[0045] Examples of measuring devices used in differential scanning calorimetry (DSC) include the DSC220C manufactured by Seiko Instruments Inc. In DSC testing, there are no particular limitations on the methods used to plot the DSC curve, to obtain the first-order differential curve from the DSC curve, to perform smoothing, or to determine the desired peak temperature. For example, when using this measuring device, the curve can be plotted based on data obtained using the device. In doing so, analytical software capable of mathematical processing can be used. Examples of analytical software include EXSTAR6000, manufactured by Seiko Instruments Inc. Regarding testing conditions, a heating rate of 15°C / min and a cooling rate of 15°C / min are preferred. Values ​​obtained under these conditions are used. The glass transition start temperature, intermediate temperature, inflection point temperature, and termination temperature are observed during testing. The intermediate temperature is used as the glass transition temperature (Tg) of the resin emulsion particles.

[0046] Furthermore, the Fox equation is as follows.

[0047] 1 / Tg=Σ(Wm / Tgm) / 100

[0048] In this equation, Tg represents the glass transition temperature, Wm represents the content (mass%) of monomer m in the monomer component constituting the resin component, and Tgm represents the glass transition temperature (absolute temperature: K) of the homopolymer of monomer m.

[0049] The glass transition temperature is determined by substituting the content of each monomer relative to the total amount of all monomers in the resin used to form the resin emulsion particles and the glass transition temperature of the homopolymer of each monomer into the equation. For example, the glass transition temperatures of the homopolymers that can be used in this method are as follows: acrylic acid homopolymer, 95°C; methacrylic acid homopolymer, 130°C; methyl methacrylate homopolymer, 105°C; styrene homopolymer, 100°C; cyclohexyl methacrylate homopolymer, 83°C; n-butyl methacrylate homopolymer, 20°C; 2-ethylhexyl acrylate homopolymer, -70°C; n-butyl acrylate homopolymer, -56°C; hydroxyethyl methacrylate homopolymer, 55°C; acrylamide homopolymer, 165°C; and 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine homopolymer, 130°C.

[0050] The resin emulsion particles preferably have acidic functional groups. The preferred acidic functional group is a carboxyl group (-COOH). The content of acidic functional groups is preferably from 0.06% to 3% by mass relative to 100% by mass of the resin emulsion particles. Based on the content of structural units derived from monomers each having an acidic functional group, the content of acidic functional groups is preferably from 0.1% to 5% by mass relative to 100% by mass of the resin emulsion particles. The preferred range for the content of carboxyl groups is the same as that for acidic functional groups.

[0051] By adjusting the content of carboxyl groups and acidic functional groups in the resin emulsion particles to values ​​within those ranges, even at low heating temperatures in inkjet textile printing, the ink can provide printed images with excellent uniformity and excellent wash fastness. For example, the content of acidic functional groups, such as carboxyl groups, in the resin emulsion particles can be adjusted by regulating the composition of the monomers used in the polymerization process for preparing the resin emulsion particles.

[0052] The acid value of the resin emulsion particles is preferably 0.5 to 50 mg KOH / g, more preferably 0.8 to 40 mg KOH / g. The preferred range of acid value due to carboxyl groups in the resin emulsion particles is the same as the preferred range of acid value described above. By adjusting the acid value of the resin emulsion particles and the acid value due to carboxyl groups to values ​​within the aforementioned ranges, even when using low heating temperatures in inkjet textile printing, the ink of the present invention can provide images with excellent uniformity and excellent wash fastness.

[0053] From the perspective of further improving water resistance and adhesion, the weight-average molecular weight of the resin component constituting the resin emulsion particles is preferably 50,000 or more, more preferably 300,000 or more, still more preferably 550,000 or more, and particularly preferably 600,000 or more. From the perspective of improving film-forming properties and water resistance, the upper limit of the weight-average molecular weight of the resin component is preferably 5,000,000 or less.

[0054] The weight-average molecular weight values ​​mentioned above are weight-average molecular weights (converted to polystyrene) determined using gel permeation chromatography [product number: HLC-8120GPC, manufactured by TosohCorp.; columns, TSKgel G-5000HXL and TSKgel GMHXL-L arranged in tandem].

[0055] There are no particular restrictions on the structure of the resin emulsion particles. Each particle can be homogeneous in overall composition, or it can have a core / shell structure consisting of a core and a shell that differ in composition and / or properties. The core / shell structure is not limited to a two-layer structure and can consist of three or more layers. Among these, a core / shell structure consisting of two or more layers is preferred, which enables an improved balance between the elongation and hardness of the coating film.

[0056] The resin emulsion particles have preferably been dispersed and stabilized using a surfactant. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and conventionally known surfactants can be used. Any one of the surfactants can be used alone, or two or more of the surfactants can be used in combination.

[0057] The surfactants are preferably nonionic or anionic. Surfactants having polymerizable groups in their molecules are also preferred. Examples of polymerizable groups include groups each having an olefinically unsaturated double bond. Particularly preferred surfactants are nonionic surfactants or anionic surfactants containing polymerizable groups. Surfactants containing polymerizable groups are also known as reactive emulsifiers. Polymerizing emulsifiers can be used as surfactants.

[0058] Examples of anionic surfactants include: alkyl sulfates, such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonates, such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate, and sodium alkyl(diphenyl ether) disulfonate; alkyl aryl sulfonates, such as ammonium dodecylbenzene sulfonate and sodium dodecylnaphthalene sulfonate; polyoxyethylene alkyl sulfonates; polyoxyethylene alkyl sulfates; polyoxyethylene alkyl aryl sulfates; dialkyl sulfosuccinates; aryl sulfonic acid / formalin condensates; fatty acid salts, such as ammonium silicate and sodium stearate; allyl sulfates or their salts, such as bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate, propylene alkyl sulfosuccinate, (meth)acrylate polyoxyethylene sulfonate, (meth)acrylate polyoxyethylene phosphate, and sulfonates of allyloxymethyl alkyloxypolyoxyethylene; allyloxymethyl alkoxyethyl polyoxyethylene sulfates; and polyoxyalkylene ether ammonium sulfates. However, anionic surfactants are not limited to these examples.

[0059] Examples of nonionic surfactants include: polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, condensates of poly(ethylene glycol) and poly(propylene glycol), sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, condensates of ethylene oxide and aliphatic amines, and polyoxyalkylene alkylene ethers. However, nonionic surfactants are not limited to these examples.

[0060] Examples of cationic surfactants include alkylammonium salts, such as dodecyl ammonium chloride. However, cationic surfactants are not limited to these examples. Examples of amphoteric surfactants include betaine ester-type emulsifiers. However, amphoteric surfactants are not limited to these examples.

[0061] Examples of polymeric emulsifiers include: poly((meth)acrylates) such as poly(sodium acrylate), poly(vinyl alcohol), polyvinylpyrrolidone, poly((meth)acrylate hydroxyalkyl esters) such as poly(hydroxyethyl acrylate), and copolymers comprising one or more comonomer units derived from the monomers constituting these polymers. However, polymeric emulsifiers are not limited to these examples.

[0062] Examples of reactive emulsifiers include: propylene alkyl sulfonyl succinate, (meth)acrylate polyoxyethylene sulfonate, (meth)acrylate polyoxyethylene phosphate (e.g., trade name Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.), polyoxyethylene (alkylpropylene phenyl ether) sulfonate (e.g., trade name Aqualon HS-10, manufactured by Dai-ich Kogyo Seiyaku Co., Ltd.), allyloxymethylalkyloxy polyoxyethylene sulfonate (e.g., trade name Aqualon KH-10, manufactured by Dai-ich Kogyo Seiyaku Co., Ltd.), polyoxyethylene styrene-modified propylene phenyl ether sulfate ammonium salt (e.g., trade name Aqualon AR-10, manufactured by Dai-ich Kogyo Seiyaku Co., Ltd.), and polyoxyethylene styrene-modified propylene phenyl ether (e.g., trade name Aqualon AN-10, manufactured by Dai-ich Kogyo Seiyaku Co., Ltd.). Allyloxymethylnonylphenoxyethyl hydroxy polyoxyethylene sulfonates (e.g., trade name ADEKA REASOAP SE-10, manufactured by ADEKA Corp.), allyloxymethylalkoxyethyl hydroxy polyoxyethylene sulfates (e.g., trade names ADEKA REASOAP SR-10 and SR-30, manufactured by ADEKA Corp.), bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonates (e.g., trade name Antox MS-60, manufactured by Nippon Nyukazai Co., Ltd.), allyloxymethylalkoxyethyl hydroxy polyoxyethylene (e.g., trade name ADEKA REASOAP ER-20, manufactured by ADEKA Corp.), polyoxyethylene alkylpropylene phenyl ethers (e.g., trade name Aqualon RN-20, manufactured by Dai-ich Kogyo Seiyaku Co., Ltd.), methyl alkoxyethyl hydroxy polyoxyethylene sulfonates ... (manufactured by Co., Ltd.), and allyloxymethylnonylphenoxyethyl hydroxy polyoxyethylene (e.g., trade name ADEKA REASOAP NE-10, manufactured by ADEKA Corp.). However, reactive emulsifiers are not limited to these examples.

[0063] The resin emulsion particles are made of resin, and there are no particular limitations on the resin. Examples of resins include: vinyl resins, (meth)acrylic resins, olefin resins, urethane resins, fluoropolymers, silicone resins, epoxy resins, phenoxy resins, phenolic resins, and xylene resins.

[0064] Among these, polymers obtained by polymerizing one or more monomers containing olefinic unsaturated double bonds are preferred. In other words, polymers that each comprise structural units derived from one or more monomers containing olefinic unsaturated double bonds are preferred. When the resin is a polymer obtained by polymerizing one or more monomers containing olefinic unsaturated double bonds, the content of acidic functional groups, such as carboxyl groups, and hydrophobic monomers can be arbitrarily designed.

[0065] Examples of monomers containing olefinically unsaturated double bonds include: vinyl monomers, such as vinyl acetate, vinyl chloride, acrylonitrile, acrylamide, and vinyl benzoate; (meth)acrylic monomers, such as (meth)acrylates and (meth)acrylic acid; styrene monomers, such as styrene, α-methylstyrene, and chloromethylstyrene; and olefin monomers, such as ethylene and propylene. Other examples include: maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, monomethyl maleate, monobutyl maleate, monomethyl itaconic acid, and monobutyl itaconic acid.

[0066] The resin of the resin emulsion particles is preferably a polymer / copolymer obtained by polymerizing / copolymerizing one or more of the monomers.

[0067] Examples include: vinyl acetate polymers, vinyl chloride polymers, ethylene / vinyl acetate copolymers, polystyrene, styrene / acrylonitrile copolymers, styrene / butadiene copolymers, acrylonitrile / butadiene / styrene copolymers, acrylonitrile / ethylene / styrene copolymers, acrylonitrile / vinyl chloride / styrene copolymers, polyethylene, polypropylene, ethylene / propylene copolymers, ethylene / vinyl acetate / (meth)acrylate copolymers, (meth)acrylate copolymers, (meth)acrylate / (meth)acrylate copolymers, (meth)acrylate / styrene copolymers, (meth)acrylate / (meth)acrylate / styrene copolymers, ethylene / vinyl acetate / (meth)acrylate copolymers, (meth)acrylate / carbamate copolymers, and acrylonitrile / (meth)acrylate / styrene copolymers.

[0068] From the perspective that copolymers enable the inks of the present invention to readily provide printed textiles with excellent rubbing fastness and texture when applied to fabrics containing highly hydrophobic fibers (e.g., polypropylene fibers) as the main component, the preferred copolymers are those obtained by copolymerizing a monomer composition containing at least one or more (meth)acrylate monomers and one or more styrene monomers as monomers containing olefinic unsaturated double bonds. This copolymer is also referred to as an acrylic / styrene polymer. Examples of acrylic / styrene polymers include: (meth)acrylate / styrene copolymers, (meth)acrylate / (meth)acrylate / styrene copolymers, and acrylonitrile / (meth)acrylate / styrene copolymers.

[0069] The monomers used to form the 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 is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 95% by mass or more, and especially preferably 100% by mass, relative to a total of 100% by mass of all monomers used to form the acrylic / styrene polymer.

[0070] In other words, the acrylic / styrene polymer only needs to include structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and may contain structural units other than these. However, relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer, the total content of structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass.

[0071] As a monomer of (meth)acrylic acid, one or more monomers selected from conventionally known (meth)acrylates and (meth)acrylic acid can be used.

[0072] Examples of (meth)acrylates include: alkyl (meth)acrylates, such as 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, cyclohexyl (meth)acrylate, n-lauryl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and isobornyl (meth)acrylate; and fluoroalkyl (meth)acrylates, such as (meth)propylene. Trifluoroethyl acrylate, tetrafluoropropyl acrylate, and octafluoropentyl acrylate; aralkyl acrylates, such as benzyl acrylate, phenylethyl acrylate, methyl benzyl acrylate, and naphthyl acrylate; hydroxyalkyl acrylates, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, and 4-hydroxybutyl acrylate; epoxy-containing methacrylates, such as glycidyl acrylate and α-methylglycidyl acrylate; alkoxyalkyl-containing methacrylates. Acrylates, such as methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, and trimethylolpropane tripropoxy(meth)acrylate; silyl-containing (meth)acrylates, such as γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropylhydroxysilane, and γ-(meth)acryloyloxypropylmethylhydroxysilane; carbonyl-containing (meth)acrylates, such as (meth)acryloyloxyalkyl acrolein, acetone (meth)acrylate, diacetone (meth)acrylate, 2-hydroxypropyl (meth)acrylate acetoacetate, 1,4-butanediol acrylate acetoacetate, and (meth)acrylate... 2-(acetylacetoxy)ethyl acrylate; azacyclopropane-containing (meth)acrylates, such as (meth)acryloylaziroxide and 2-azacyclopropane ethyl acrylate; oxygen-containing (meth)acrylates, such as (methoxy)(meth)acrylate (di)ethylene glycol esters, for example, ethylene glycol (meth)acrylate, methoxy(meth)acrylate, diethylene glycol (meth)acrylate and methoxy(meth)acrylate (diethylene glycol); and piperidinyl-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 may be selected and used.

[0073] Another type of (meth)acrylate that can be used is the polyfunctional (meth)acrylate. Examples of polyfunctional (meth)acrylates include di(meth)acrylates of polyols having 1 to 10 carbon atoms, such as 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, propylene oxide-modified neopentyl glycol di(meth)acrylate, and tri(meth)acrylate. Propylene glycol di(meth)acrylate; alkyl di(meth)acrylates wherein the added alkyl oxide having 2 to 4 carbon atoms is in a molar number of 2 to 50, such as poly(ethylene glycol) di(meth)acrylates wherein the added ethylene oxide is in a molar number of 2 to 50, poly(propylene glycol) di(meth)acrylates wherein the added propylene oxide is in a molar number of 2 to 50, and tri(propylene glycol) di(meth)acrylates; tri(meth)acrylates of polyols having 1 to 10 carbon atoms, such as ethoxylated glycerol tri(meth)acrylates, 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; tetra(meth)acrylates of polyols having 1 to 10 carbon atoms, such as pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and bis(trimethylolpropane) tetra(meth)acrylate; polyols having 1 to 10 carbon atoms Penta(meth)acrylates, such as pentaerythritol penta(meth)acrylate and dipentaerythritol (monohydroxy) penta(meth)acrylate; hexa(meth)acrylates of polyols having 1 to 10 carbon atoms, such as pentaerythritol hexa(meth)acrylate; bisphenol A di(meth)acrylate, 2-(2'-vinyloxyethoxyethyl) acrylate, and epoxy-containing (meth)acrylates, such as epoxy (meth)acrylates; and polyfunctional (meth)acrylates, such as urethane (meth)acrylates.

[0074] (Meth)acrylic acid is preferably acrylic acid or methacrylic acid.

[0075] Examples of styrene-based monomers include styrene, α-methylstyrene, p-methylstyrene, tert-butylstyrene, chlorostyrene, vinyltoluene, and 2-styrylethyltrimethoxysilane. Other styrene-based monomers that may be used are styrene monomers that each comprise a benzene ring having an alkyl group (e.g., methyl or tert-butyl) or a functional group (e.g., nitro, nitrile, alkoxy, acyl, sulfone, or hydroxyl or halogen atom). Among such styrene-based monomers, styrene is preferred from the viewpoint of improved water resistance.

[0076] Another type of styrene monomer that can be used is the polyfunctional styrene monomer. Preferred examples of polyfunctional styrene monomers include divinylbenzene.

[0077] Relative to a total content of 100% by mass of one or more acrylic monomers and one or more styrene monomers, the content of one or more styrene monomers used to form the acrylic / styrene polymer is preferably 1% to 55% by mass, more preferably 5% to 50% by mass, and still more preferably 10% to 45% by mass. By adjusting the content of one or more styrene monomers to values ​​within this range, inks can easily provide printed textiles with even better texture or excellent wash fastness.

[0078] The acrylic / styrene polymer is preferably obtained by copolymerizing a monomer composition containing one or more (meth)acrylic monomers and one or more styrene monomers in a ratio preferably within the range.

[0079] The acrylic / styrene polymer is preferably a polymer having carboxyl groups, and the content of carboxyl groups is preferably from 0.06% to 3% by mass relative to 100% by mass of resin emulsion particles. The content of carboxyl groups relative to 100% by mass of structural units derived from monomers having carboxyl groups is preferably from 0.1% to 5% by mass relative to 100% by mass of resin emulsion particles.

[0080] The carboxyl group is preferably derived from (meth)acrylic acid. Therefore, it is preferable that the structural units derived from (meth)acrylic acid monomers, which are constituent components of the acrylic / styrene polymer, comprise one or more structural units derived from (meth)acrylic acid. More preferably, the structural units simultaneously comprise one or more structural units derived from any (meth)acrylic ester and one or more structural units derived from (meth)acrylic acid.

[0081] The content of structural units derived from (meth)acrylic acid monomers as constituent components of the acrylic acid / styrene polymer is preferably 0.1% to 5% by mass, more preferably 0.2% to 4% by mass, and still more preferably 1% to 3% by mass, relative to the total content of structural units derived from (meth)acrylic acid monomers and structural units derived from styrene monomers in a total content of 100% by mass.

[0082] The (meth)acrylic monomers used to form acrylic / styrene polymers preferably contain one or more (meth)acrylic acids, and more preferably contain one or more (meth)acrylates and one or more (meth)acrylic acids.

[0083] The content of (meth)acrylic acid in the monomers used to form the acrylic / styrene polymer is preferably 0.1% to 5% by mass, more preferably 0.2% to 4% by mass, and still more preferably 1% to 3% by mass, relative to a total content of 100% by mass of (meth)acrylic acid monomers and styrene monomers.

[0084] In addition to containing (meth)acrylic acid, the (meth)acrylic monomers used to form the acrylic / styrene polymer preferably also contain (meth)acrylates. Preferably, the contained (meth)acrylates include one or more alkyl (meth)acrylates and one or more hydroxyalkyl (meth)acrylates. More preferably, the (meth)acrylic monomers simultaneously contain one or more alkyl (meth)acrylates and one or more hydroxyalkyl (meth)acrylates.

[0085] The alkyl methacrylates contained herein are preferably those in which each alkyl group has 1 to 18 carbon atoms. More preferably, they are alkyl methacrylates in which each alkyl group has 4 to 12 carbon atoms. A further preferred mode is the use of two or more of the alkyl methacrylates described herein with different numbers of carbon atoms. Examples include: a combination of alkyl (meth)acrylates having 1 to 5 carbon atoms in the alkyl group and alkyl (meth)acrylates having 6 to 18 carbon atoms in the alkyl group; a combination of alkyl (meth)acrylates having one carbon atom in the alkyl group and alkyl (meth)acrylates having 8 to 18 carbon atoms in the alkyl group; a combination of alkyl (meth)acrylates having one carbon atom in the alkyl group, alkyl (meth)acrylates having 4 to 6 carbon atoms in the alkyl group, and alkyl (meth)acrylates having 8 to 18 carbon atoms in the alkyl group; and a combination of alkyl (meth)acrylates having 2 to 6 carbon atoms in the alkyl group and alkyl (meth)acrylates having 8 to 12 carbon atoms in the alkyl group. Hydroxyalkyl (meth)acrylates are more preferably hydroxyalkyl (meth)acrylates where each hydroxyalkyl chain has 1 to 18 carbon atoms, and even more preferably hydroxyalkyl (meth)acrylates where each hydroxyalkyl chain has 2 to 4 carbon atoms.

[0086] Monomers used to form acrylic / styrene polymers may also include monomers other than (meth)acrylic acid monomers and styrene-based monomers. Examples of other monomers include acrylonitrile, vinyl acetate, and acrylamide. Examples of other monomers also 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.

[0087] The acrylic / styrene polymer is preferably an acrylic / styrene polymer obtained by copolymerizing two or more preferred monomers in a preferred ratio, and is preferably a polymer containing structural units derived from the preferred monomers in a proportion corresponding to the preferred monomer ratio.

[0088] The resin emulsion particles that form the ink of the present invention are preferably resin emulsion particles containing an acrylic / styrene polymer as the main component of the resin. These particles are also referred to as acrylic / styrene polymer emulsion particles.

[0089] The preferred embodiments of the resin emulsion particles, which are constituent components of the ink of the present invention, have been described above regarding their shape, average particle size, glass transition temperature, content of acidic functional groups, content of carboxyl groups and acid value, weight-average molecular weight, particle structure, surfactant, etc. These preferred embodiments can be applied directly to acrylic / styrene polymer emulsion particles.

[0090] Acrylic / styrene polymer emulsion particles can be prepared by conventionally known emulsion polymerization methods. The preferred types, combinations, and proportions of monomers used in the emulsion polymerization are the same as those described above regarding the preferred modes or embodiments for forming the acrylic / styrene polymer. That is, acrylic / styrene polymer emulsion particles can be prepared by emulsion polymerization of monomers in an aqueous medium in the presence of an emulsifier, said monomers comprising (meth)acrylic monomers and styrene monomers, and optionally also comprising other monomers containing olefinic unsaturated double bonds. The emulsifier used can be any conventionally known emulsifier. The emulsifier used can be any of the surfactants mentioned above, and its preferred embodiments are the same as those of the surfactants.

[0091] In the emulsion obtained by emulsion polymerization, the content of residual monomers is preferably less than 100 ppm by mass of the emulsion. The content of residual monomers can be determined, for example, by gas chromatography. Preferably, a polymerization initiator is added after the polymerization reaction and the maturation is extended so that the content of residual monomers in the emulsion after maturation is less than 100 ppm.

[0092] <Compounds containing an oxazolin group>

[0093] The ink of this invention contains a compound containing an oxazoline group.

[0094] In this invention, the term "compound containing an oxazoline group" refers to a compound having two or more oxazoline groups in its molecule. Examples of compounds containing an oxazoline group include: 2,2'-bis(2-oxazoline), 2,2'-methylenebis(2-oxazoline), 2,2'-ethylidenebis(2-oxazoline), 2,2'-trimethylenebis(2-oxazoline), 2,2'-tetramethylenebis(2-oxazoline), 2,2'-hexamethylenebis(2-oxazoline), 2,2'-octamethylenebis(2-oxazoline), 2,2'-ethylidenebis(4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylbis(2-oxazoline), 2,2'-m-phenylbis(2-oxazoline), 2,2'-m-phenylbis(4,4'-dimethyl-2-oxazoline), bis(2-oxazoline-cyclohexane) sulfide, bis(2-oxazoline-norbornene) sulfide, and polymers containing an oxazoline group. However, compounds containing an oxazoline group are not limited to these examples. Any one of these compounds containing an oxazoline group can be used alone, or two or more of them can be used in combination.

[0095] Among compounds containing an oxazoline group, water-soluble oxazoline-containing compounds are preferred from the perspective of their excellent crosslinking properties. Also preferred are polymers containing an oxazoline group. Polymers containing an oxazoline group can be prepared by conventionally known preparation methods. Examples of such methods include polymerizing a monomeric component comprising one or more addition-polymerizable oxazolines, or a monomeric component simultaneously comprising an addition-polymerizable oxazoline and a monomer that can copolymerize with the addition-polymerizable oxazoline. The copolymerizable monomer is preferably a monomer without functional groups that react with the oxazoline group and that can copolymerize with the addition-polymerizable oxazoline. Examples include the aforementioned monomers containing olefinic unsaturated double bonds without functional groups that react with the oxazoline group. Examples include: vinyl monomers, such as vinyl acetate, vinyl chloride, acrylonitrile, acrylamide, and vinyl benzoate; (meth)acrylate monomers, such as (meth)acrylates; styrene monomers, such as styrene, α-methylstyrene, and chloromethylstyrene; and olefin monomers, such as ethylene and propylene.

[0096] 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.

[0097] Water-soluble oxazoline-containing polymers are preferred among those containing oxazoline groups. These water-soluble oxazoline-containing polymers can be prepared by the same method used to prepare oxazoline-containing polymers. Examples of water-soluble oxazoline-containing polymers include polymers consisting of a main chain as an acrylic polymer, an acrylic / styrene polymer, etc., and side chains containing oxazoline groups.

[0098] Commercially available products containing oxazoline groups can be used. Examples include water-soluble polymers, such as Epocros WS-500 and Epocros WS-700 manufactured by Nippon Shokubai Co., Ltd., and emulsion polymers, such as Epocros K-2010, Epocros K-2020, and Epocros K-2030 manufactured by Nippon Shokubai Co., Ltd. Among these, Epocros WS-500 and Epocros WS-700, manufactured by Nippon Shokubai Co., Ltd., are preferred as they are water-soluble polymers.

[0099] The content of the oxazoline-containing compound in the ink of the present invention is from 0.5% to 10% by mass relative to 100% by mass of resin emulsion particles. This range is preferred, primarily from the perspective of rubbing fastness. Its content is preferably 5% by mass or less.

[0100] It is speculated that compounds containing oxazoline groups interact or chemically react with components contained in the ink of the present invention (e.g., resin emulsion particles, pigments, or dispersants for pigments), thereby acting as crosslinking agents even at low temperatures and forming a tough coating film.

[0101] <Aqueous Media>

[0102] The ink of the present invention comprises an aqueous medium. The term "aqueous medium" in this invention refers to a solvent containing water. The water content in the aqueous medium is preferably from 10% to 100% by mass. More preferably, the water content is 25% by mass or more, still more preferably 60% by mass or more, and particularly preferably 90% by mass or more. The remainder is preferably an organic solvent.

[0103] Aqueous media may contain organic solvents. Examples of organic solvents include: glycols, such as propylene glycol, 1,3-propanediol, glycerol, dipropylene glycol, tripropylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; ethers of monoethylene glycol, 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; and ethers of monopropylene glycol, such as monopropylene glycol monomethyl ether, monopropylene glycol monoethyl ether, monopropylene glycol monopropyl ether, monopropylene glycol monoisopropyl ether, and monopropylene glycol monoisopropyl ether. Glycol monobutyl ether and propylene glycol monoisobutyl ether; poly(ethylene glycol) ethers, such as poly(ethylene glycol) monomethyl ether (with EO molar number = 2 to 10, preferably 2 to 4), poly(ethylene glycol) monoethyl ether (with EO molar number = 2 to 10, preferably 2 to 4), poly(ethylene glycol) monopropyl ether (with EO molar number = 2 to 10, preferably 2 to 4), poly(ethylene glycol) monoisobutyl ether (with EO molar number = 2 to 10, preferably 2 to 4). Isopropyl ether, poly(ethylene glycol) monobutyl ether (with an added EO molar number of 2 to 10, preferably 2 to 4) and poly(ethylene glycol) monoisobutyl ether (with an added EO molar number of 2 to 10, preferably 2 to 4); poly(propylene glycol) ethers, such as poly(propylene glycol) monomethyl ether (with an added EO molar number of 2 to 10, preferably 2 to 4), poly(propylene glycol) monoethyl ether (with an added EO molar number of 2 to 10, preferably 2 to 4), poly(propylene glycol) (… Monopropyl ether (with an added EO in molar numbers of 2 to 10, preferably 2 to 4), monoisopropyl ether (with an added EO in molar numbers of 2 to 10, preferably 2 to 4), monobutyl ether (with an added EO in molar numbers of 2 to 10, preferably 2 to 4), and monoisobutyl ether (with an added EO in molar numbers of 2 to 10, preferably 2 to 4); and heterocyclic compounds, such as 2-pyrrolidone and N-methyl-2-pyrrolidone.

[0104] Preferred among these are propylene glycol, glycerol, diethylene glycol, triethylene glycol, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monobutyl ether, poly(ethylene glycol) monobutyl ether (with an added EO molar number of 2 to 4), and 2-pyrrolidone. More preferred are propylene glycol, triethylene glycol, poly(ethylene glycol) monobutyl ether (with an added EO molar number of 2 to 4), and 2-pyrrolidone. Any one of these organic solvents can be used alone, or two or more of them can be used in combination.

[0105] <Composition>

[0106] The resin emulsion particles in the ink of the present invention comprise 10% to 20% by mass relative to 100% by mass of the ink. This range is preferred from the perspective of both improving the rubbing fastness of the image formed by low-temperature heat treatment during inkjet textile printing and the jetting stability of the ink during printing. The content is preferably 10.5% by mass or more, but less than 18.0% by mass.

[0107] There is no particular limitation on the pigment content in the ink of the present invention, but it is preferably 1 to 20% by mass relative to 100% by mass of ink. If the pigment content is less than 1% by mass, the ink may be insufficient in terms of coloring or covering performance. If the content exceeds 20% by mass, it may lead to a decrease in texture. More preferably, the pigment content is 2% by mass or more, but less than 18% by mass.

[0108] The content of the aqueous medium in the ink of the present invention is preferably 55% to 89% by mass, more preferably 70% to 85% by mass, relative to 100% by mass of the ink of the present invention.

[0109] In the ink of the present invention, from the viewpoint of improving the opacity or coloring of the formed or printed image, the pigment content is preferably 10% to 80% by mass, more preferably 15% to 75% by mass, relative to a total content of 100% by mass of pigment, resin emulsion particles and oxazoline-containing compounds.

[0110] <Other Ingredients>

[0111] The ink of the present invention may contain components other than the essential components mentioned above (pigments, resin emulsion particles, aqueous media), unless such inclusion would impede the purpose of the invention. For example, the ink may contain suitable 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. Preferably, leveling agents are surfactants based on acetylene glycol, organosilicon, or fluorinated chemicals. Polyether-modified organosilicon compounds are preferred among these.

[0112] When any of the other ingredients are added, their content is not particularly limited, but ideally it is 2% by mass or less, preferably 1% by mass or less, relative to 100% by mass of the ink of the present invention. From the viewpoint of producing an additive effect, this content is preferably 0.01% by mass or more, more preferably 0.05% by mass or more.

[0113] <Method for preparing inkjet textile printing ink of the present invention>

[0114] There are no particular limitations on the method used to prepare the ink of the present invention. Although the ink can be prepared, for example, by mixing pigments, resin emulsion particles, oxazoline-containing compounds and aqueous media, the following is a preferred preparation example.

[0115] First, an emulsion containing resin emulsion particles and a pigment dispersion are prepared. The pigment dispersion is preferably a pigment dispersion obtained by dispersing the pigment in an aqueous medium. The pigment dispersion can be prepared, for example, by mixing the pigment and dispersant with an aqueous medium (e.g., water) and dispersing the mixture using a bead mill or similar method. There is no particular limitation on the pigment content in the pigment dispersion, but it is preferably 15% to 65% by mass relative to 100% by mass of the pigment dispersion. On the other hand, as described above, an emulsion containing resin emulsion particles can be prepared by conventionally known emulsion polymerization methods. There is no particular limitation on the resin emulsion particle content in the emulsion, but it is preferably 30% to 65% by mass relative to 100% by mass of the emulsion. Although emulsions obtained by emulsion polymerization typically contain emulsifiers for emulsification, such as surfactants, such emulsions can be used as is for preparing the ink of the present invention.

[0116] Next, the pigment dispersion, emulsion, oxazoline-containing compound, and optionally an aqueous medium are mixed together. During mixing, the oxazoline-containing compound can be used as is, or a solution obtained by diluting the compound with, for example, an aqueous medium can be used. There are no particular limitations on the method or order of mixing the components. For example, methods can be used where: the emulsion is mixed with the pigment dispersion, and then the oxazoline-containing compound is mixed with it; methods can be used where the pigment dispersion is mixed with the oxazoline-containing compound, and then the emulsion is mixed with it; methods can be used where the emulsion is mixed with the oxazoline-containing compound, and then the pigment dispersion is mixed with it; and methods can be used where the pigment dispersion, emulsion, and oxazoline-containing compound are mixed together almost simultaneously.

[0117] To adjust the concentration of each component in the ink of the present invention, or to adjust the properties of the ink, an aqueous medium, or a component of the aqueous medium, namely water and an organic solvent, or a mixture thereof, may be mixed in. Other components besides those mentioned above, such as additives, may be further mixed in. The timing of mixing these components (aqueous medium, additives, etc.) may be appropriately selected. Centrifugation, filtration using a filter, etc., may be performed as needed.

[0118] The ink of the present invention was obtained by the above preparation method. The ink comprises pigment, resin emulsion particles, oxazoline-containing compound and aqueous medium, and may also contain other components, such as additives, as needed.

[0119] The ink of the present invention described above is suitable for printing on fabrics using an inkjet printer. Using the ink of the present invention in inkjet textile printing can provide articles on fabrics with any desired image (e.g., text, design, or drawing) printed on them. Due to the above configuration, the ink for inkjet textile printing of the present invention provides printed images with excellent rubbing fastness even when used in inkjet textile printing at low heating temperatures. Therefore, the use of the ink of the present invention in inkjet printing on fabrics or other textiles not only achieves energy savings in the drying step but also enables the formation and printing of images with excellent rubbing fastness even on fabrics containing materials with low heat resistance temperatures (e.g., polypropylene fibers and polyester fibers).

[0120] 2. A method for manufacturing a printed matter comprising a fabric having an image printed thereon.

[0121] Various methods can be used to manufacture printed materials (textiles) using the inkjet textile printing ink of the present invention. A preferred manufacturing method is described. This method is for manufacturing printed materials comprising a fabric on which an image is printed, the method including an image forming step in which the inkjet textile printing ink of the present invention is adhered to the fabric using an inkjet printer to form an image. This manufacturing method is also referred to as the printed material manufacturing method of the present invention. A transfer textile printing method in which the inkjet textile printing ink of the present invention is used can also be employed. The transfer textile printing method can be a conventionally known method. Examples of transfer textile printing methods include a method comprising the following steps: a transfer paper manufacturing step, wherein inkjet textile printing ink of the present invention is sprayed onto a transfer paper substrate using an inkjet printer and dried as needed, thereby producing a transfer paper on which an image is formed; a transfer step, wherein the transfer paper manufactured in the transfer paper manufacturing step is stacked on a fabric and the laminate is heated and / or pressurized, thereby transferring the image formed on the transfer paper to the fabric; and a peeling step, wherein the transfer paper is peeled off from the fabric on which the image has been transferred in the transfer step.

[0122] In this specification, the term "fabric" means any of all textile products (including cloth, textiles, etc.) formed from natural and / or synthetic fibers. Examples include textiles, nonwovens, and knitted fabrics. There are no particular limitations on the fibers constituting a fabric, and examples include natural fibers, chemical fibers, and mixtures thereof.

[0123] Preferred examples of natural fibers include silk, cotton, and wool. Examples of chemical fibers include synthetic fibers, regenerated fibers, and semi-synthetic fibers. Preferred examples of synthetic fibers include polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, polyethylene fibers, polypropylene fibers, and Vinylon fibers. Preferred examples of regenerated fibers include rayon. Preferred examples of semi-synthetic fibers include acetate and triacetate.

[0124] Preferred among these are fabrics comprising cotton, polyester, and polypropylene fibers, respectively. As will be described later, the preferred heat treatment temperature varies depending on the type of fiber constituting the fabric. Even in the case of fabrics comprising polyester fibers as the main component or fabrics comprising polypropylene fibers as the main component and for which a low heat treatment temperature should be used, printed textiles with excellent rubbing fastness can be manufactured by using the ink of the present invention. Even in the case of fabrics (such as cotton fabrics) that are conventionally heat-treated at 160°C to fix the image and ensure fastness, the use of the ink of the present invention enables the manufacture of printed textiles with excellent fastness even by processing at a lower heating temperature.

[0125] There are no particular limitations on the inkjet printer used in the image forming step and the transfer paper manufacturing step, and conventionally known inkjet printers can be used. The inkjet printer can be any type of printer operating in piezoelectric mode, thermal mode, charge change control mode (continuous jet mode), etc. A piezoelectric mode inkjet printer is particularly preferred. When using a piezoelectric mode inkjet printer, there are no particular limitations on inkjet conditions, etc., and suitable conditions can be selected based on the properties of the ink according to the invention, the type of fabric, the type of image to be printed, etc. The viscosity of the ink for inkjet textile printing according to the present invention is preferably in the range of 2 to 20 mPa / s. The surface tension of the ink is preferably in the range of 25 to 45 mN / m.

[0126] In the image forming step and the transfer paper manufacturing step, the ink of the present invention, which has been ejected from the nozzle opening of the inkjet printing head, adheres to the fabric surface and the transfer paper substrate respectively to form an image.

[0127] The printing method of the present invention preferably includes a step of heating the fabric on which the image is formed in the image forming step at a temperature above room temperature (also referred to as a heat treatment step). On the other hand, the transfer textile printing method preferably includes a step of heating the fabric on which the image is transferred from 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 accelerate the removal of volatile components from the ink (e.g., aqueous media) contained in the image formed on the fabric, and can accelerate image fixation. Furthermore, heat treatment promotes film formation (melt bonding) by resin emulsion particles contained in the ink, thereby improving image adhesion, etc. In addition, the reaction for generating reaction product (C), which will be described later, is readily performed.

[0128] The heat treatment step can be performed simultaneously with the image forming step or the transfer step, or it can be performed after the image forming step or the transfer step, or a combination of both methods can be used. Examples of methods for performing the heat treatment step simultaneously with the image forming step or the transfer step include methods in which the image forming step or the transfer step is performed while the fabric is being heated. Preferred examples of heat treatment methods in the case of performing the heat treatment step after the image forming step or the transfer step include: heating using a drying oven; heating using a hot press; heating using an infrared lamp; and methods in which steam (e.g., atmospheric pressure steam or high pressure steam) is used. The preferred heating methods among these are performing the heat treatment step after the image forming step or the transfer step because there is a possibility that performing both steps simultaneously may lead to disordered flow.

[0129] The heating temperature used in each heat treatment step is preferably between 90 and 180°C. The upper limit is more preferably below 150°C, still more preferably below 130°C, particularly preferably below 120°C, and the lower limit is more preferably above 95°C, still more preferably above 100°C. In the heat treatment step, the recommended heating temperature and heating time vary depending on the fibers constituting the fabric. For example, the temperature is 160°C for cotton, 125°C for polypropylene, and 110°C for polyester, and the time for all these materials is 5 minutes or less, preferably 3 minutes or less, more preferably 2 minutes or less. The printed textiles (prints obtained by forming images on fabric) obtained through the heat treatment step can be washed with water and dried.

[0130] By means of the printing method of the present invention and the transfer textile printing method wherein the inkjet textile printing ink of the present invention is used, even when using low heating temperatures, printed textiles (including printed matter on fabrics on which images are formed) in which printed images have excellent rubbing fastness can be manufactured in an environmentally friendly manner with reduced energy consumption.

[0131] From the perspective of obtaining printed textiles with excellent rubbing fastness in a short time, as mentioned above, the heating temperature is preferably 90°C or higher. However, the heating temperature in the heat treatment step is not limited to this range, and can be, for example, a temperature near room temperature, such as 15 to 25°C. Even when using heat treatment at such a temperature, the rubbing fastness of the printed image can be improved by heating for a longer period of time. From the perspective of shortening the heating time, the temperature is preferably 30°C or higher, more preferably 50°C or higher, and still more preferably 90°C or higher.

[0132] Ambient temperature is, for example, 15 to 25°C, and room temperature, as the actual indoor temperature, is generally considered to be about 15 to 25°C.

[0133] In this specification, printing only needs to include the image forming step, in which an inkjet textile printing ink is applied to a fabric using an inkjet printer to form an image. Images printed by the printing method of the present invention and the transfer textile printing method using the inkjet textile printing ink of the present invention may undergo heat treatment at a temperature above room temperature, or may not undergo any heat treatment at a temperature above room temperature.

[0134] 3. Articles with printed images and articles with attached images.

[0135] The present invention also provides articles having printed images. The articles having printed images provided by the present invention are articles obtained by forming a printed image on a portion or all of a fabric using the inkjet textile printing ink of the present invention, wherein the printed image comprises pigment and resin, and the resin comprises a reaction product (C) between an acrylic / styrene polymer (A) having carboxyl groups and a compound (B) containing oxazoline groups. The printed image is preferably a printed image in which the resin acts as a binder and is dispersed in the resin and contains pigment. The inkjet textile printing ink preferably contains an acrylic / styrene polymer (A) having carboxyl groups.

[0136] Even when the ink is not heated at a temperature above room temperature, the reaction product (C) is generated by drying at room temperature. The higher the temperature, the greater the extent of the reaction. Although the rate of reaction product (C) formation is higher when the ink is heated at a temperature above room temperature, it is believed that the reaction product (C) will gradually form over time even when drying at room temperature.

[0137] The present invention also provides articles having an attached image. The articles having an attached image provided by the present invention are articles comprising a fabric and an image, said image being attached to a portion or all of said fabric and comprising pigment and resin, characterized in that said resin comprises a reaction product (C) between an acrylic / styrene polymer (A) having a carboxyl group and a compound (B) containing an oxazoline group. The attached image comprises pigment and resin. Preferably, the attached image is an attached image in which the resin acts as a binder and is dispersed in the resin and contains pigment.

[0138] The statement "including fabric and images attached to part or all of the fabric and containing pigments and resins" means that images containing pigments and resins are adhesive and have excellent rubbing fastness.

[0139] <Resin>

[0140] The resin comprises a reaction product (C) between an acrylic / styrene polymer (A) having carboxyl groups and a compound (B) containing oxazoline groups. The acrylic / styrene polymer (A) having carboxyl groups is described below. The acrylic / styrene polymer (A) having carboxyl groups is also referred to as polymer (A).

[0141] Examples of monomers (e.g., styrene monomers and (meth)acrylic monomers) used to form polymer (A) include the same monomers used to form acrylic / styrene polymers having carboxyl groups (preferred embodiments of resins that are resin emulsion particles constituting the ink of the present invention). Specific examples are omitted here.

[0142] The acrylic / styrene polymer in polymer (A) is a copolymer of acrylic monomers and styrene monomers. Polymer (A) only needs to include structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and may contain other structural units besides these. However, relative to a total of 100% by mass of all structural units constituting polymer (A), the total content of structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100 mol%.

[0143] There are no particular limitations on the structural units derived from styrene monomers in polymer (A). However, the content of structural units derived from (meth)acrylic acid monomers and structural units derived from styrene monomers is preferably 1% to 55% by mass, more preferably 5% to 50% by mass, and still more preferably 10% to 45% by mass, relative to a total content of 100% by mass. When the content of styrene monomers is within this range, articles with printed images and articles with attached images are likely to be articles with excellent texture or excellent wash fastness (e.g., printed textiles).

[0144] The content of carboxyl groups in polymer (A) is preferably 0.06% to 3% by mass relative to 100% by mass of polymer (A). The carboxyl groups are preferably derived from (meth)acrylic acid. Therefore, polymer (A) is more preferably a polymer (A) containing structural units derived from (meth)acrylic acid. In polymer (A), the content of structural units derived from (meth)acrylic acid monomers is preferably 0.1% to 5% by mass, more preferably 0.2% to 4% by mass, and still more preferably 1% to 3% by mass, relative to 100% by mass of structural units derived from (meth)acrylic acid monomers and structural units derived from styrene monomers.

[0145] Polymer (A) preferably further contains structural units derived from (meth)acrylates. Particularly preferably, polymer (A) contains structural units derived from alkyl (meth)acrylates and / or structural units derived from hydroxyalkyl (meth)acrylates. More preferably, polymer (A) contains both structural units derived from alkyl (meth)acrylates and structural units derived from hydroxyalkyl (meth)acrylates.

[0146] In the structural unit derived from alkyl (meth)acrylate, the alkyl group contained therein includes alkyl groups having 1 to 18 carbon atoms, more preferably alkyl groups having 4 to 12 carbon atoms. It is also preferred to have embodiments in which the alkyl group includes two or more alkyl groups with different numbers of carbon atoms. Examples include: embodiments in which the alkyl group includes alkyl groups having 1 to 5 carbon atoms and alkyl groups having 6 to 18 carbon atoms; embodiments in which the alkyl group includes alkyl groups having one carbon atom and alkyl groups having 8 to 18 carbon atoms; embodiments in which the alkyl group includes alkyl groups having one carbon atom, alkyl groups having 4 to 6 carbon atoms, and alkyl groups having 8 to 18 carbon atoms; and embodiments in which the alkyl group includes alkyl groups having 2 to 6 carbon atoms and alkyl groups having 8 to 12 carbon atoms. In the structural unit derived from hydroxyalkyl (meth)acrylate, the hydroxyalkyl group is preferably a hydroxyalkyl group having 1 to 18 carbon atoms, more preferably a hydroxyalkyl group having 2 to 4 carbon atoms.

[0147] The structural units in polymer (A) may include structural units other than those derived from (meth)acrylic acid monomers and those derived from styrene monomers. Examples of other structural units include those derived from monomers such as acrylonitrile, vinyl acetate, and acrylamide.

[0148] Compound (B) containing an oxazoline group will be described. Compound (B) containing an oxazoline group and its preferred embodiments are the same as the oxazoline-containing compounds and their preferred embodiments contained in the ink of the present invention, and the description given above is applicable here. Therefore, its description is omitted.

[0149] The reaction product (C) between polymer (A) and compound (B) containing an oxazoline group is described. The reaction product (C) is generated by the reaction of the carboxyl group of polymer (A) with the oxazoline group of compound (B). Preferably, the reaction product (C) has an amide ester bond formed through this reaction. There is no particular limitation on the content of the amide ester bond, but it is preferably 0.05% to 5% by mass relative to 100% by mass of resin. More preferably, it is 0.1% to 3% by mass. There is no particular limitation on the content of the reaction product (C) in the resin, but it is preferably 0.1% to 50% by mass relative to 100% by mass of resin. More preferably, it is 0.2% to 40% by mass, and still more preferably, it is 0.3% to 30% by mass.

[0150] In addition to the reaction product (C), the resin preferably also contains a polymer (A). The inclusion of polymer (A) readily imparts an excellent texture to the fabric. The content of polymer (A) in the 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, still more preferably 70% by mass or more, and the upper limit is more preferably 99.8% by mass or less, still more preferably 99.7% by mass or less, and even more preferably 99% by mass or less.

[0151] The resin may also contain a compound (B) containing an oxazoline group. The content of polymer (B) in the resin is preferably 0% to 5% by mass relative to 100% by mass of the resin. More preferably, it is 0% to 2% by mass, and still more preferably 0% to 1% by mass.

[0152] Pigments

[0153] The pigments and their preferred embodiments are the same as those constituting the ink of the present invention, and the descriptions given above are applicable here. Therefore, their descriptions are omitted.

[0154] <Printed Images and Attached Images>

[0155] Both printed and attached images contain resin and pigment.

[0156] The total content of resin and pigment in the printed image and the attached image is preferably 80% to 100% by mass, relative to 100% by mass of the image. More preferably, the total content is 90% to 100% by mass, and still more preferably 95% to 100% by mass or higher.

[0157] The resin content in the printed image and the attached 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 still more preferably 30% to 85% by mass.

[0158] The printed image may have been printed on part or all of the fabric.

[0159] The attached image may have been attached to part or all of the fabric.

[0160] There are no particular limitations on the thickness of the printed image and the attached image. However, their thickness is preferably 0.1 to 1,000 μm, more preferably 0.3 to 500 μm, and still more preferably 0.5 to 100 μm. The thickness value can be taken from the measurement obtained by means of, for example, a laser microscope.

[0161] <Fabrics>

[0162] The definitions of fabrics in articles with printed images and articles with attached images of the present invention, as well as the specific usable materials, are the same as those described above in "Method for Manufacturing Fabrics with Printed Images," and the above description is applicable here. Their preferred embodiments are also the same. That is, fabrics comprising cotton, polyester fibers, and polypropylene fibers are preferred. More preferably are fabrics comprising cotton as a main component, fabrics comprising polyester fibers as a main component, and fabrics comprising polypropylene fibers as a main component.

[0163] The article having a printed image and the article having an attached image of the present invention have been described.

[0164] Even when the heat treatment step during printing is performed at low temperatures, the article of the present invention with printed images exhibits excellent rubbing fastness. The preferred mode of the heat treatment step is the same as those described above in the section on the method of manufacturing printed matter of the present invention.

[0165] The article with the attached image of the present invention has excellent friction fastness.

[0166] The statement "possesses excellent rubbing fastness" means that when the product is subjected to dry and wet rubbing tests using a Type II testing machine and undyed standard fabric of No. 3-1 cotton under a load of 200g and 100 cycles, according to the method specified in JIS L0849, and then evaluated using the color change / fading gray scale, the product will be rated at level 3-4 or higher in both the dry and wet rubbing tests.

[0167] The articles of the present invention having printed images and the articles of the present invention having attached images can be manufactured using, for example, a particularly preferred embodiment of the inkjet textile printing ink of the present invention. In doing so, it is preferred to employ the method of the present invention for manufacturing fabrics having printed images or the transfer method for manufacturing fabrics having printed images.

[0168] Example

[0169] The present invention will be described in more detail below with reference to embodiments, but the present invention is not limited to the embodiments. Unless otherwise specified, “parts” means “parts by mass” and “%” means “% by mass”.

[0170] The following measurement and evaluation methods are used.

[0171] <Average particle size of resin emulsion particles>

[0172] The average particle size of the resin emulsion particles was determined by detecting the resin emulsion using a particle size distribution analyzer based on dynamic light scattering (product number: FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.) and by using the value obtained from the detection through the cumulative method.

[0173] <Average particle size of pigment>

[0174] The average particle size of the pigment was determined by detecting the pigment dispersion using a particle size distribution analyzer based on dynamic light scattering (product number: FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.) and by using the value obtained from the detection by the cumulative amount method.

[0175] <Ink viscosity>

[0176] The inks obtained in the examples and comparative examples were tested using an E-type viscometer TPE-100 (manufactured by TokiSangyo Co., Ltd.) at rotor R24, 0.8 degrees and 25°C.

[0177] <Ink Storage Stability>

[0178] The inks obtained in the examples and comparative examples were encapsulated in sealed containers and stored in a constant temperature room at 50°C for 30 days, and then evaluated according to the following criteria.

[0179] ⊙: Viscosity change during storage is less than 5%.

[0180] ○: Viscosity changes by 5% to 10% during storage.

[0181] Δ: Viscosity changes by 11% to 20% during storage.

[0182] ×: The ink gelled during storage.

[0183] <Jet Stability>

[0184] The inks obtained in the examples and comparative examples were introduced into a textile printing press MMP-TX13 (manufactured by Mastermind Co., Ltd.), and nozzle-test printing (where grid lines were printed by sequentially ejecting ink from all 180 nozzles) was performed on PET film. Deviations and omissions in the printed pattern were visually inspected. Furthermore, the printing head was covered and allowed to stand for one week, then used for nozzle-test printing again, and the deviations and omissions were visually evaluated. Inks rated Δ or × were deemed insufficient in terms of jetting stability.

[0185] ⊙: No deviations or omissions were found in the initial printing and after one week.

[0186] ○: There are one or two deviations or omissions in the worse print run compared to the initial print run and the print run one week later.

[0187] Δ: There are three or four deviations or omissions in the worse print run between the initial print run and the print run one week later.

[0188] ×: There are more than five deviations or omissions in the worse print run between the initial print run and the print run one week later.

[0189] <Friction resistance>

[0190] According to the method specified in JIS L0849, using a Type II testing machine and an undyed standard fabric of No. 3-1 cotton, dry and wet rubbing tests were conducted on the fabrics with printed images obtained in the examples and comparative examples under a load of 200g and 100 cycles, respectively. The results were then evaluated using a color change / fading grayscale. For Example 7, which used white ink, the ink was printed on a cotton fabric (a 100% cotton black T-shirt produced by Hanes, Inc.), and the fabric was evaluated. Fabrics with printed images rated Δ or × were deemed insufficient in terms of rubbing fastness.

[0191] ⊙: A rating of 4-5 or higher in both dry and wet friction tests.

[0192] ○: In both dry and wet friction tests, the level is 3-4 to 4.

[0193] Δ: In both dry and wet friction tests, it is a grade of 2-3 to 3.

[0194] ×: Grade 2 or lower in dry or wet friction tests.

[0195] <Wash fastness>

[0196] The fabrics with printed images obtained in the examples and comparative examples were subjected to ten regular washes using a household washing machine (washing conditions: normal mode wash → rinse → spin dry → dry; liquid detergent Ariel (manufactured by P&G Co.)), and the degree of fading was evaluated using color change / fading grayscale.

[0197] ⊙: Level 4-5 to Level 5.

[0198] ○: Level 3-4 to Level 4.

[0199] Δ: Level 2-3 to Level 3.

[0200] ×: Level 2 or lower.

[0201] <Texture>

[0202] The fabrics with printed images obtained in the examples and comparative examples were evaluated by touch.

[0203] ⊙: Fabrics with printed images are easy to bend and have a softness close to that of the original fabric.

[0204] ○: Fabrics with printed images are easy to bend, but feel slightly stiffer than the original fabric.

[0205] Δ: Fabrics with printed images feel stiff to the touch.

[0206] ×: Fabric with printed images is too stiff to bend freely.

[0207] <Example of Emulsion Preparation>

[0208] [Example 1 of emulsion preparation]

[0209] 252 parts of deionized water were introduced into a flask equipped with a dropping funnel, stirrer, nitrogen inlet tube, thermometer, and reflux condenser. A dropping preemulsion was prepared, consisting of 437 parts of deionized water, 80 parts of a 25% aqueous solution of emulsifier (trade name ADEKA REASOAP SR-10, manufactured by ADEKA Corp.), 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 preemulsion (equivalent to 3% of all monomer components) were placed in the dropping funnel and introduced into the flask. While gently supplying nitrogen, the temperature was raised to 80°C, and 30 parts of a 5% aqueous solution of ammonium persulfate was added to initiate polymerization. Subsequently, the remaining portion of the dropping preemulsion and 30 parts of the 5% aqueous solution of ammonium persulfate were uniformly added dropwise into the flask over 240 minutes. After the addition was complete, the contents of the flask were maintained at 80°C for 180 minutes. 25% ammonia and deionized water were added to adjust the pH to 8.5 and the solids content to 50%, thus terminating the polymerization. The resulting liquid reaction mixture was cooled to room temperature and then filtered through a 300-mesh metal sieve to obtain the emulsion. The emulsion resin particles had a styrene monomer content of 35%, a Tg of -21°C, and an average particle size of 200 nm.

[0210] [Example 2 of emulsion preparation]

[0211] Except that 7 parts of the pre-emulsion (equivalent to 0.5% of all monomer components) were introduced into the flask, the emulsion was obtained in the same manner as in Emulsion Preparation Example 1. The emulsion resin particles had a styrene monomer content of 35%, a Tg of -21°C, and an average particle size of 310 nm.

[0212] [Example 3 of emulsion preparation]

[0213] Except that 87 parts of the pre-emulsion (equivalent to 6% of all monomer components) were introduced into the flask, the emulsion was obtained in the same manner as in Emulsion Preparation Example 1. The emulsion resin particles had a styrene monomer content of 35%, a Tg of -21°C, and an average particle size of 140 nm.

[0214] [Example 4 of emulsion preparation]

[0215] Except that the amount of styrene in the pre-emulsion was changed to 50 parts and 300 parts of methyl methacrylate were newly added, the emulsion was obtained in the same manner as in Emulsion Preparation Example 1. The styrene monomer content of the emulsion resin particles was 5%, the Tg was -20°C, and the average particle size of the emulsion was 200 nm.

[0216] [Example 5 of emulsion preparation]

[0217] Except that the amount of cyclohexyl methacrylate in the pre-emulsion was changed to 0 parts and the amount of styrene was changed to 200 parts, the emulsion was obtained in the same manner as in Emulsion Preparation Example 1. The styrene monomer content of the emulsion resin particles was 20%, the Tg was -22°C, and the average particle size of the emulsion was 210 nm.

[0218] [Example 6 of emulsion preparation]

[0219] Except that the amount of 2-ethylhexyl methacrylate in the 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 emulsion was obtained in the same manner as in Emulsion Preparation Example 1. The styrene monomer content of the emulsion resin particles was 50%, the Tg was -5°C, and the average particle size of the emulsion was 200 nm.

[0220] <Example of Pigment Dispersion Preparation>

[0221] [Example 1: Preparation of Pigment Dispersions]

[0222] Three parts of dispersant Joncryl 687 (manufactured by BASF AG), 1.3 parts of dimethylaminoethanol, and 81 parts of deionized water were stirred and mixed at 70°C. Subsequently, 15 parts of blue pigment CIPigmentBlue 15:3 (LIONOL BLUE FG-7330, manufactured by Toyo Ink Mfg. Co., Ltd.) and 0.1 parts of surfactant Olfin D-10PG (manufactured by Nissin Chemical Industry Co., Ltd.) were dispersed using a bead mill filled with 0.5 mm zirconium oxide beads at 50% by volume. The resulting mixture was filtered through a 1 μm pore size filter (MCP-1-C10S, manufactured by Advantec Co., Ltd.) to obtain a blue pigment dispersion with a pigment content of 15%. The average particle size of this dispersion was 90 nm.

[0223] [Example 2 of pigment dispersion preparation]

[0224] Except for replacing the blue pigment with a metal-free CI pigment blue 16 (produced by Tokyo Kasei Kogyo Co., Ltd.), the same procedure as in Pigment Dispersion Preparation Example 1 was performed, thereby obtaining a blue pigment dispersion with a pigment content of 15%. The average particle size of this dispersion was 95 nm.

[0225] [Example 3 of pigment dispersion preparation]

[0226] Five parts of dispersant Discoat N-14 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), six parts of propylene glycol, 70 parts of deionized water, and 100 parts of titanium dioxide CR-95 (manufactured by Ishihara Sangyo Kaisha, Ltd.) were dispersed in a ball mill using 0.5 mm zirconium oxide beads filled at 50% by volume. This yielded a white pigment dispersion with a pigment content of 55%. The average particle size of this dispersion was 330 nm.

[0227] <Example>

[0228] [Example 1]

[0229] (Ink preparation)

[0230] Thirty parts (15 parts by weight of emulsion particles) of the emulsion obtained in Emulsion Preparation Example 1, 23 parts (15 parts by weight of pigment) of the pigment dispersion obtained in Pigment Dispersion Preparation Example 1, 1.2 parts (0.3 parts by weight of solids) of Epocros WS-700 (manufactured by Nippon Shokubai KagakuKogyo Co., Ltd.; solids content: 25%), 2 parts of diethylene glycol monobutyl ether, 15 parts of triethylene glycol, 0.3 parts of surfactant KF-6011 (manufactured by Shin-Etsu Chemical Co., Ltd.), and 28.5 parts of deionized water were mixed together. The mixture was filtered through a filter with a pore size of 1 μm (MCP-1-C10S, manufactured by Advantec Co., Ltd.) to prepare ink (1).

[0231] (Image formed by inkjet printing)

[0232] The resulting ink (1) was introduced into an inkjet textile printer MMP-TX13 (manufactured by Mastermind Co., Ltd.), and solid printing was performed on cotton fabric (a 100% cotton white T-shirt manufactured by Hanes, Inc.) with blue ink at 1,440 dpi × 1,440 dpi, a printing speed of 8, and a printing depth of 120 mm × 120 mm, thereby forming an image on the fabric. The fabric with the image formed on it was then heat-treated for 90 seconds in a hot air drying oven at 110°C to obtain fabric (1) with the printed image.

[0233] [Examples 2 to 13 and Comparative Examples 1 to 8]

[0234] Except for the changes in the types and amounts of raw materials in Example 1 (Ink Preparation) as shown in Tables 1 to 3, and the adjustment of the deionized water feed amount to obtain a total of 100 parts, the inks (2) to (13) of Examples 2 to 13 and the inks (c1) to (c8) of Comparative Examples 1 to 8 were prepared in the same manner as in Example 1. The oxazoline-containing compounds, carbodiimide-containing compounds, and terminated isocyanate compounds used and shown in Tables 1 to 3 are Epocros WS-700 (manufactured by Nippon Shokubai Co., Ltd.; solids content: 25%), Carbodilite SV-02 (manufactured by Nisshinbo Chemical Inc.; solids content: 40%), and Byhydur BL2867 (manufactured by Sumika Covestro Urethane Co., Ltd.; solids content: 38%).

[0235] Next, images were formed using the inks of the examples and comparative examples by inkjet printing in the same manner as in Example 1, thereby obtaining fabrics (2) to (13) and fabrics (c1) to (c8) each having an image formed thereon. The types of fabrics and heat treatment conditions used in the examples and comparative examples are shown in Tables 1 to 3.

[0236] The polyester fabric used is a 100% polyester white T-shirt manufactured by Gunze Ltd. The polypropylene fabric used is a fabric composed of 100% polypropylene fibers. Fabrics (2) to (13) and fabrics (c1) to (c8) are fabrics each having a printed image, and are obtained by inkjet printing in the same manner as in Example 1, followed by heat treatment under the heat treatment conditions shown in Tables 1 to 3 in the same manner as in Example 1.

[0237] Tables 1 to 3 show the inks prepared in the examples and comparative examples, their inkjet performance, and the evaluation results of the fabrics with printed images.

[0238] [Table 1]

[0239]

[0240] [Table 2]

[0241]

[0242] [Table 3]

[0243]

[0244] As shown in Tables 1 and 2, the inks (1) to (13) obtained in Examples 1 to 13 each have excellent jetting stability, and although the heat treatment conditions are 110°C and 90 seconds or 110°C and 60 seconds, the fabrics (1) to (13) with images printed by inkjet printers using the corresponding inks each have excellent rubbing fastness of the printed images.

[0245] Furthermore, the fabrics (1) to (13) obtained in Examples 1 to 13 are each fabrics with printed images attached and have excellent rubbing fastness.

[0246] Industrial applicability

[0247] The inkjet textile printing ink of the present invention can be used as an inkjet textile printing ink that, when used for inkjet textile printing, not only provides a printed image with excellent rub fastness even when inkjet textile printing is performed at low heating temperatures, but also has excellent jetting stability.

Claims

1. An inkjet textile printing ink, wherein the inkjet textile printing ink comprises pigment, resin emulsion particles, an oxazoline-containing compound, and an aqueous medium, wherein... The resin emulsion particles have an average particle size of 150 nm or more. The resin emulsion particles contain 10% to 20% by mass relative to 100% by mass of the inkjet textile printing ink. The oxazoline-containing compound is a compound having two or more oxazoline groups in its molecule, and the content of the oxazoline-containing compound is from 0.5% to 10% by mass relative to 100% by mass of the resin emulsion particles. The resin emulsion particles have acidic functional groups, and the resin constituting the resin emulsion particles comprises a polymer obtained by polymerizing monomers containing olefinic unsaturated double bonds.

2. The ink for inkjet textile printing according to claim 1, wherein the pigment comprises a white pigment having an average particle size of 100 to 500 nm.

3. The ink for inkjet textile printing according to claim 1, wherein the pigment comprises a white pigment having an average particle size of 150 to 450 nm.

4. The ink for inkjet textile printing according to claim 1, wherein the pigment comprises a white pigment having an average particle size of 200 to 400 nm.

5. The ink for inkjet textile printing according to claim 1, wherein the pigment comprises a coloring pigment having an average particle size of 20 to 200 nm.

6. The ink for inkjet textile printing according to claim 1, wherein the pigment comprises a coloring pigment having an average particle size of 40 to 150 nm.

7. The ink for inkjet textile printing according to claim 1, wherein the pigment comprises a coloring pigment having an average particle size of 50 to 100 nm.

8. The ink for inkjet textile printing according to claim 1, wherein the average particle size of the resin emulsion particles is 180 nm or more and 330 nm or less.

9. The ink for inkjet textile printing according to claim 1, wherein the average particle size of the resin emulsion particles is greater than 200 nm and less than 300 nm.

10. The ink for inkjet textile printing according to claim 1, wherein the average particle size of the resin emulsion particles is 210 nm or more and 300 nm or less.

11. The ink for inkjet textile printing according to claim 1, wherein the glass transition temperature of the resin emulsion particles is above -50°C and below 0°C.

12. The ink for inkjet textile printing according to claim 1, wherein the glass transition temperature of the resin emulsion particles is above -40°C and below -10°C.

13. The ink for inkjet textile printing according to claim 1, wherein the glass transition temperature of the resin emulsion particles is above -40°C and below -15°C.

14. The ink for inkjet textile printing according to claim 1, wherein the acidic functional group is a carboxyl group.

15. The ink for inkjet textile printing according to claim 1, wherein the acidic functional group includes a carboxyl group.

16. The ink for inkjet textile printing according to claim 14, wherein the content of the acidic functional group is from 0.06% to 3% by mass relative to 100% by mass of the resin emulsion particles.

17. The ink for inkjet textile printing according to claim 14, wherein the content of the acidic functional group is from 0.1% to 5% by mass relative to 100% by mass of the resin emulsion particles, based on the content of structural units derived from monomers each having the acidic functional group.

18. The ink for inkjet textile printing according to claim 15, wherein the content of the carboxyl group is from 0.06% to 3% by mass relative to 100% by mass of the resin emulsion particles.

19. The ink for inkjet textile printing according to claim 15, wherein the content of the carboxyl group is from 0.1% to 5% by mass relative to 100% by mass of the resin emulsion particles, based on the content of structural units derived from each monomer having the carboxyl group.

20. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the acid value of the resin emulsion particles is 0.5 to 50 mgKOH / g.

21. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the acid value of the resin emulsion particles is 0.8 to 40 mgKOH / g.

22. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 50,000 or more.

23. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 300,000 or more.

24. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 550,000 or more.

25. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 600,000 or more.

26. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 5,000,000 or less.

27. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the resin emulsion particles have a uniform composition throughout the particles.

28. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the resin emulsion particles have a core / shell structure consisting of a core and a shell that are different in composition and / or properties.

29. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the resin emulsion particles are dispersed and stabilized using a surfactant.

30. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the resin emulsion particles are dispersed and stabilized using a nonionic surfactant or anionic surfactant.

31. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the resin emulsion particles are dispersed and stabilized using a nonionic surfactant having polymerizable groups or an anionic surfactant having polymerizable groups.

32. The inkjet textile printing ink according to claim 1, wherein the monomer containing an olefinic unsaturated double bond comprises at least one selected from the group consisting of: Vinyl acetate, vinyl chloride, acrylonitrile, acrylamide, vinyl benzoate, (meth)acrylate, (meth)acrylic acid, styrene, α-methylstyrene, chloromethylstyrene, ethylene, propylene, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, monomethyl maleate, monobutyl maleate, monomethyl itaconic acid, and monobutyl itaconic acid.

33. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the resin constituting the resin emulsion particles comprises at least one selected from the group consisting of: 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 / vinyl chloride / styrene copolymer, polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / vinyl acetate / (meth)acrylate copolymer, (meth)acrylate copolymer, (meth)acrylate / (meth)acrylate copolymer, (meth)acrylate / styrene copolymer, (meth)acrylate / (meth)acrylate / styrene copolymer, ethylene / vinyl acetate / (meth)acrylate copolymer, (meth)acrylate / urethane copolymer, and acrylonitrile / (meth)acrylate / styrene copolymer.

34. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the resin emulsion particles comprise an acrylic / styrene polymer.

35. The ink for inkjet textile printing according to claim 34, wherein the acrylic / styrene polymer comprises at least one selected from the group consisting of: (meth)acrylate / styrene copolymer, (meth)acrylate / (meth)acrylate / styrene copolymer and acrylonitrile / (meth)acrylate / styrene copolymer.

36. The ink for inkjet textile printing according to claim 34, wherein the acrylic / styrene polymer comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 50% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer.

37. The ink for inkjet textile printing according to claim 34, wherein the acrylic / styrene polymer comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 80% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer.

38. The ink for inkjet textile printing according to claim 34, wherein the acrylic / styrene polymer comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 95% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer.

39. The ink for inkjet textile printing according to any one of claims 36-38, wherein the content of the styrene monomer in the monomer used to form the acrylic / styrene polymer is from 1% to 55% by mass relative to the total content of the (meth)acrylic monomer and the styrene monomer, which is 100% by mass.

40. The ink for inkjet textile printing according to any one of claims 36-38, wherein the content of the styrene monomer in the monomer used to form the acrylic / styrene polymer is from 5% to 50% by mass relative to the total content of the (meth)acrylic monomer and the styrene monomer, which is 100% by mass.

41. The ink for inkjet textile printing according to any one of claims 36-38, wherein the content of the styrene monomer in the monomer used to form the acrylic / styrene polymer is from 10% to 45% by mass relative to the total content of the (meth)acrylic monomer and the styrene monomer, which is 100% by mass.

42. The ink for inkjet textile printing according to claim 34, wherein the acrylic / styrene polymer comprises a polymer having a carboxyl group.

43. The ink for inkjet textile printing according to claim 42, wherein the content of the carboxyl groups in the acrylic / styrene polymer is from 0.06% to 3% by mass relative to 100% by mass of the resin emulsion particles.

44. The ink for inkjet textile printing according to claim 42 or 43, wherein the content of the carboxyl group in the acrylic / styrene polymer is from 0.1% to 5% by mass relative to 100% by mass of the resin emulsion particles, based on the content of structural units derived from monomers having carboxyl groups.

45. The ink for inkjet textile printing according to claim 34, wherein the structural units derived from (meth)acrylic monomers constituting the acrylic / styrene polymer comprise one or more structural units derived from (meth)acrylic acid.

46. ​​The ink for inkjet textile printing according to claim 34, wherein the structural units derived from (meth)acrylic monomers constituting the acrylic / styrene polymer comprise one or more structural units derived from (meth)acrylates and one or more structural units derived from (meth)acrylic acid.

47. The ink for inkjet textile printing according to claim 46, wherein the (meth)acrylate comprises 2-ethylhexyl acrylate and / or hydroxyethyl methacrylate.

48. The ink for inkjet textile printing according to claim 34, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer is from 0.1% to 5% by mass relative to the total content of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers, which are 100% by mass.

49. The ink for inkjet textile printing according to claim 34, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer is from 0.2% to 4% by mass relative to the total content of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers, which are 100% by mass.

50. The ink for inkjet textile printing according to claim 34, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer is from 1% to 3% by mass relative to the total content of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers, which are 100% by mass.

51. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the oxazoline-containing compound comprises a water-soluble oxazoline-containing compound.

52. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the oxazoline-containing compound comprises a water-soluble oxazoline-containing polymer or an emulsion-type oxazoline-containing polymer.

53. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the oxazoline-containing compound comprises a water-soluble oxazoline-containing polymer.

54. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the oxazoline-containing compound comprises an oxazoline-containing polymer.

55. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the content of the oxazoline-containing compound is from 0.5% to 10% by mass relative to 100% by mass of the resin emulsion particles.

56. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the content of the oxazoline-containing compound is 0.5% to 5% by mass relative to 100% by mass of the resin emulsion particles.

57. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the water content in the aqueous medium is from 10% by mass to 100% by mass.

58. The ink for inkjet textile printing according to claim 57, wherein the water content in the aqueous medium is from 25% by mass to 100% by mass.

59. The ink for inkjet textile printing according to claim 57, wherein the water content in the aqueous medium is 60% to 100% by mass.

60. The ink for inkjet textile printing according to claim 57, wherein the water content in the aqueous medium is 90% to 100% by mass.

61. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the aqueous medium comprises an organic solvent.

62. The ink for inkjet textile printing according to claim 61, wherein the organic solvent comprises at least one selected from the group consisting of: glycols, ethers of monoethylene glycol, ethers of monopropylene glycol, ethers of polyethylene glycol, ethers of poly(propylene glycol), and heterocyclic compounds.

63. The ink for inkjet textile printing according to claim 61, wherein the organic solvent comprises at least one selected from the group consisting of: propylene glycol, glycerol, diethylene glycol, triethylene glycol, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monobutyl ether, polyethylene glycol monobutyl ether in a molar number of 2 to 4 of added EO, and 2-pyrrolidone.

64. The ink for inkjet textile printing according to claim 61, wherein the organic solvent comprises at least one selected from the group consisting of: propylene glycol, triethylene glycol, polyethylene glycol monobutyl ether in a molar number of 2 to 4 of added EO, and 2-pyrrolidone.

65. The inkjet textile printing ink according to any one of claims 1 to 19, wherein the content of the resin emulsion particles is from 10.5% to 18% by mass relative to 100% by mass of the inkjet textile printing ink.

66. The inkjet textile printing ink according to any one of claims 1 to 19, wherein the pigment content is from 1% to 20% by mass relative to 100% by mass of the inkjet textile printing ink.

67. The inkjet textile printing ink according to any one of claims 1 to 19, wherein the pigment content is from 2% to 18% by mass relative to 100% by mass of the inkjet textile printing ink.

68. The inkjet textile printing ink according to any one of claims 1 to 19, wherein the content of the aqueous medium is from 55% to 89% by mass relative to 100% by mass of the inkjet textile printing ink.

69. The inkjet textile printing ink according to any one of claims 1 to 19, wherein the content of the aqueous medium is 70% to 85% by mass relative to 100% by mass of the inkjet textile printing ink.

70. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the pigment content is from 10% to 80% by mass relative to the total content of 100% by mass of the pigment, the resin emulsion particles and the oxazoline-containing compound.

71. The ink for inkjet textile printing according to any one of claims 1 to 19, wherein the pigment content is 15% to 75% by mass relative to the total content of 100% by mass of the pigment, the resin emulsion particles and the oxazoline-containing compound.

72. A method for manufacturing a printed matter in which an image is printed on a fabric, the method comprising an image forming step in which the image is formed by applying inkjet textile printing ink according to any one of claims 1 to 71 to the fabric using an inkjet printer.

73. A method for manufacturing a printed matter in which an image is printed on a fabric, the method comprising: The transfer paper manufacturing step involves using an inkjet printer to spray ink for inkjet textile printing according to any one of claims 1 to 71 onto a transfer paper substrate to produce a transfer paper on which an image is formed. A transfer step, wherein the transfer paper is stacked on the fabric and heated and / or pressed to transfer the image formed on the transfer paper to the fabric; as well as The peeling step involves peeling the transfer paper from the fabric onto which the image has been transferred in the transfer step.

74. The method of manufacturing a printed matter in which an image is printed on a fabric according to claim 73, wherein in the transfer paper manufacturing step, after the ink is sprayed onto the transfer paper substrate, the sprayed ink is dried to form the image.

75. An article having a printed image, said article having a printed image is obtained by forming said printed image on a portion or all of a fabric with inkjet textile printing ink according to any one of claims 1 to 71, wherein The printed image contains pigments and resin, and The resin comprises a reaction product (C) between an acrylic / styrene polymer (A) having carboxyl groups and a compound (B) containing oxazoline groups.

76. The article having a printed image according to claim 75, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 50% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer (A).

77. The article having a printed image according to claim 75, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 80% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer.

78. The article having a printed image according to claim 75, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 95% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer.

79. The article having a printed image according to claim 75, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 100% by mass relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer (A).

80. The article having a printed image according to claim 76, wherein the content of the structural units derived from styrene monomers in the acrylic / styrene polymer (A) is from 1% to 55% by mass relative to the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers, which is 100% by mass.

81. The article having a printed image according to claim 76, wherein the content of the structural units derived from styrene monomers in the acrylic / styrene polymer (A) is from 5% to 50% by mass relative to the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers, which is 100% by mass.

82. The article having a printed image according to claim 76, wherein the content of the structural units derived from styrene monomers in the acrylic / styrene polymer (A) is from 10% to 45% by mass relative to the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers, which is 100% by mass.

83. The article having a printed image according to claim 75, wherein the content of the carboxyl group in the acrylic / styrene polymer (A) is from 0.06% to 3% by mass relative to 100% by mass of the acrylic / styrene polymer (A).

84. The article of manufacture having a printed image according to claim 75, wherein the carboxyl group is a carboxyl group derived from (meth)acrylic acid.

85. The article of manufacture having a printed image according to claim 75, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic acid.

86. The article having a printed image according to claim 85, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer (A) is from 0.1% to 5% by mass relative to the total content of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers, which is 100% by mass.

87. The article having a printed image according to claim 85, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer (A) is from 0.2% to 4% by mass relative to the total content of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers, which is 100% by mass.

88. The article having a printed image according to claim 85, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer (A) is from 1% to 3% by mass relative to the total content of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers, which is 100% by mass.

89. The article having a printed image according to any one of claims 75 to 88, wherein the acrylic / styrene polymer (A) further comprises at least one structural unit selected from alkyl methacrylates and hydroxyalkyl methacrylates.

90. The article having a printed image according to any one of claims 75 to 88, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate.

91. The article having a printed image according to any one of claims 75 to 88, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic acid, structural units derived from alkyl (meth)acrylates, and structural units derived from hydroxyalkyl (meth)acrylates.

92. The article of manufacture having a printed image according to any one of claims 75 to 88, wherein the oxazoline-containing compound (B) comprises an oxazoline-containing polymer.

93. The article having a printed image according to any one of claims 75 to 88, wherein the oxazoline-containing compound (B) comprises a water-soluble oxazoline-containing polymer or an emulsion-type oxazoline-containing polymer.

94. The article having a printed image according to any one of claims 75 to 88, wherein the oxazoline-containing compound (B) comprises a water-soluble oxazoline-containing compound.

95. The article of manufacture having a printed image according to any one of claims 75 to 88, wherein the oxazoline-containing compound (B) comprises a water-soluble oxazoline-containing polymer.

96. The article having a printed image according to any one of claims 75 to 88, wherein the reaction product (C) has an amide ester bond.

97. The article of claim 96 having a printed image, wherein the content of the amide ester bond is from 0.05% to 5% by mass relative to 100% by mass of the resin.

98. The article having a printed image according to any one of claims 75 to 88, wherein the content of the reaction product (C) is from 0.1% to 50% by mass relative to 100% by mass of the resin.

99. The article having a printed image according to any one of claims 75 to 88, wherein the content of the reaction product (C) is from 0.2% to 40% by mass relative to 100% by mass of the resin.

100. The article having a printed image according to any one of claims 75 to 88, wherein the content of the reaction product (C) is from 0.3% to 30% by mass relative to 100% by mass of the resin.

101. The article having a printed image according to any one of claims 75 to 88, wherein the resin further comprises the acrylic / styrene polymer (A).

102. The article having a printed image according to claim 101, wherein the content of the acrylic / styrene polymer (A) is from 50% to 99.9% by mass relative to 100% by mass of the resin.

103. The article having a printed image according to claim 101, wherein the content of the acrylic / styrene polymer (A) is 60% by mass or more relative to 100% by mass of the resin.

104. The article having a printed image according to claim 101, wherein the content of the acrylic / styrene polymer (A) is 70% by mass or more relative to 100% by mass of the resin.

105. The article having a printed image according to claim 101, wherein the content of the acrylic / styrene polymer (A) is 99.8% by mass or less relative to 100% by mass of the resin.

106. The article having a printed image according to claim 101, wherein the content of the acrylic / styrene polymer (A) is 99.7% by mass or less relative to 100% by mass of the resin.

107. The article having a printed image according to claim 101, wherein the content of the acrylic / styrene polymer (A) is 99% by mass or less relative to 100% by mass of the resin.

108. The article having a printed image according to any one of claims 75 to 88, wherein the resin further comprises the oxazoline-containing compound (B).

109. The article having a printed image according to claim 108, wherein the content of the oxazoline-containing compound (B) is from 0% to 5% by mass relative to 100% by mass of the resin.

110. The article of manufacture having a printed image according to claim 108, wherein the content of the oxazoline-containing compound (B) is from 0% to 2% by mass relative to 100% by mass of the resin.

111. The article of manufacture having a printed image according to claim 108, wherein the content of the oxazoline-containing compound (B) is from 0% to 1% by mass relative to 100% by mass of the resin.

112. The article of manufacture having a printed image according to any one of claims 75 to 88, wherein the pigment comprises a white pigment having an average particle size of 100 to 500 nm.

113. The article of manufacture having a printed image according to any one of claims 75 to 88, wherein the pigment comprises a white pigment having an average particle size of 150 to 450 nm.

114. The article of manufacture having a printed image according to any one of claims 75 to 88, wherein the pigment comprises a white pigment having an average particle size of 200 to 400 nm.

115. The article having a printed image according to any one of claims 75 to 88, wherein the pigment comprises a coloring pigment having an average particle size of 20 to 200 nm.

116. The article having a printed image according to any one of claims 75 to 88, wherein the pigment comprises a coloring pigment having an average particle size of 40 to 150 nm.

117. The article having a printed image according to any one of claims 75 to 88, wherein the pigment comprises a coloring pigment having an average particle size of 50 to 100 nm.

118. The article having a printed image according to any one of claims 75 to 88, wherein the total content of the resin and the pigment in the printed image is 80% to 100% by mass relative to 100% by mass of the printed image.

119. The article having a printed image according to any one of claims 75 to 88, wherein the total content of the resin and the pigment in the printed image is 90% to 100% by mass relative to 100% by mass of the printed image.

120. The article having a printed image according to any one of claims 75 to 88, wherein the total content of the resin and the pigment in the printed image is 95% to 100% by mass relative to 100% by mass of the printed image.

121. The article having a printed image according to any one of claims 75 to 88, wherein the resin content in the printed image is from 20% to 95% by mass relative to 100% by mass of the printed image.

122. The article having a printed image according to any one of claims 75 to 88, wherein the resin content in the printed image is 25% to 90% by mass relative to 100% by mass of the printed image.

123. The article having a printed image according to any one of claims 75 to 88, wherein the resin content in the printed image is 30% to 85% by mass relative to 100% by mass of the printed image.

124. The article of manufacture having a printed image according to any one of claims 75 to 88, wherein the thickness of the printed image is 0.1 to 1000 μm.

125. The article of manufacture having a printed image according to any one of claims 75 to 88, wherein the thickness of the printed image is 0.3 to 500 μm.

126. The article of manufacture having a printed image according to any one of claims 75 to 88, wherein the thickness of the printed image is 0.5 to 100 μm.

127. The article having a printed image according to any one of claims 75 to 88, wherein the fabric comprises at least one selected from the group consisting of cotton, polyester fibers and polypropylene fibers.

128. The article having a printed image according to any one of claims 75 to 88, wherein the fabric comprises at least one selected from the group consisting of cotton, polyester fibers and polypropylene fibers as a main component.

129. An article having an attached image, the article having an attached image comprising a fabric and the image, the image being attached to a portion or all of the fabric and comprising pigment and resin, and prepared using an inkjet textile printing ink according to any one of claims 1 to 71. The resin comprises a reaction product (C) between an acrylic / styrene polymer (A) having carboxyl groups and a compound (B) containing oxazoline groups.

130. The article having an attached image according to claim 129, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 50% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer (A).

131. The article having an attached image according to claim 129, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 80% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer.

132. The article having an attached image according to claim 129, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 95% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer.

133. The article having an attached image according to claim 129, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 100% by mass relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer (A).

134. The article having an attached image according to claim 130, wherein the content of the structural units derived from styrene monomers in the acrylic / styrene polymer (A) is from 1% to 55% by mass relative to the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers, which is 100% by mass.

135. The article having an attached image according to claim 130, wherein the content of the structural units derived from styrene monomers in the acrylic / styrene polymer (A) is from 5% to 50% by mass relative to the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers, which is 100% by mass.

136. The article having an attached image according to claim 130, wherein the content of the structural units derived from styrene monomers in the acrylic / styrene polymer (A) is from 10% to 45% by mass relative to the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers, which is 100% by mass.

137. The article having an attached image according to claim 129, wherein the content of the carboxyl groups in the acrylic / styrene polymer (A) is from 0.06% to 3% by mass relative to 100% by mass of the acrylic / styrene polymer (A).

138. The article having an attached image according to claim 129, wherein the carboxyl group is a carboxyl group derived from (meth)acrylic acid.

139. The article having an attached image according to claim 129, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic acid.

140. The article having an attached image according to claim 139, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer (A) is from 0.1% to 5% by mass relative to the total content of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers, which is 100% by mass.

141. The article having an attached image according to claim 139, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer (A) is from 0.2% to 4% by mass relative to the total content of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers, which is 100% by mass.

142. The article having an attached image according to claim 139, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer (A) is from 1% to 3% by mass relative to the total content of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers, which is 100% by mass.

143. The article having an attached image according to any one of claims 129 to 142, wherein the acrylic / styrene polymer (A) further comprises at least one structural unit selected from alkyl methacrylates and hydroxyalkyl methacrylates.

144. The article having an attached image according to any one of claims 129 to 142, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate.

145. The article having an attached image according to any one of claims 129 to 142, wherein the acrylic / styrene polymer (A) comprises structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate alkyl esters, and structural units derived from (meth)acrylate hydroxyalkyl alkyl esters.

146. The article having an attached image according to any one of claims 129 to 142, wherein the oxazoline-containing compound (B) comprises an oxazoline-containing polymer.

147. The article having an attached image according to any one of claims 129 to 142, wherein the oxazoline-containing compound (B) comprises a water-soluble oxazoline-containing polymer or an emulsion-type oxazoline-containing polymer.

148. The article having an attached image according to any one of claims 129 to 142, wherein the oxazoline-containing compound (B) comprises a water-soluble oxazoline-containing compound.

149. The article having an attached image according to any one of claims 129 to 142, wherein the oxazoline-containing compound (B) comprises a water-soluble oxazoline-containing polymer.

150. The article having an attached image according to any one of claims 129 to 142, wherein the reaction product (C) has an amide ester bond.

151. The article having an attached image according to claim 150, wherein the content of the amide ester bond is from 0.05% to 5% by mass relative to 100% by mass of the resin.

152. The article having an attached image according to any one of claims 129 to 142, wherein the content of the reaction product (C) is from 0.1% to 50% by mass relative to 100% by mass of the resin.

153. The article having an attached image according to any one of claims 129 to 142, wherein the content of the reaction product (C) is from 0.2% to 40% by mass relative to 100% by mass of the resin.

154. The article having an attached image according to any one of claims 129 to 142, wherein the content of the reaction product (C) is from 0.3% to 30% by mass relative to 100% by mass of the resin.

155. The article having an attached image according to any one of claims 129 to 142, wherein the resin further comprises the acrylic / styrene polymer (A).

156. The article having an attached image according to claim 155, wherein the content of the acrylic / styrene polymer (A) is from 50% to 99.9% by mass relative to 100% by mass of the resin.

157. The article having an attached image according to claim 155, wherein the content of the acrylic / styrene polymer (A) is 60% by mass or more relative to 100% by mass of the resin.

158. The article having an attached image according to claim 155, wherein the content of the acrylic / styrene polymer (A) is 70% by mass or more relative to 100% by mass of the resin.

159. The article having an attached image according to claim 155, wherein the content of the acrylic / styrene polymer (A) is 99.8% by mass or less relative to 100% by mass of the resin.

160. The article having an attached image according to claim 155, wherein the content of the acrylic / styrene polymer (A) is 99.7% by mass or less relative to 100% by mass of the resin.

161. The article having an attached image according to claim 155, wherein the content of the acrylic / styrene polymer (A) is 99% by mass or less relative to 100% by mass of the resin.

162. The article having an attached image according to any one of claims 129 to 142, wherein the resin further comprises the oxazoline-containing compound (B).

163. The article having an attached image according to claim 162, wherein the content of the oxazoline-containing compound (B) is from 0% to 5% by mass relative to 100% by mass of the resin.

164. The article having an attached image according to claim 162, wherein the content of the oxazoline-containing compound (B) is from 0% to 2% by mass relative to 100% by mass of the resin.

165. The article having an attached image according to claim 162, wherein the content of the oxazoline-containing compound (B) is from 0% to 1% by mass relative to 100% by mass of the resin.

166. The article having an attached image according to any one of claims 129 to 142, wherein the pigment comprises a white pigment having an average particle size of 100 to 500 nm.

167. The article having an attached image according to any one of claims 129 to 142, wherein the pigment comprises a white pigment having an average particle size of 150 to 450 nm.

168. The article having an attached image according to any one of claims 129 to 142, wherein the pigment comprises a white pigment having an average particle size of 200 to 400 nm.

169. The article having an attached image according to any one of claims 129 to 142, wherein the pigment comprises a coloring pigment having an average particle size of 20 to 200 nm.

170. The article having an attached image according to any one of claims 129 to 142, wherein the pigment comprises a coloring pigment having an average particle size of 40 to 150 nm.

171. The article having an attached image according to any one of claims 129 to 142, wherein the pigment comprises a coloring pigment having an average particle size of 50 to 100 nm.

172. The article having an attachment image according to any one of claims 129 to 142, wherein the total content of the resin and the pigment in the attachment image is 80% to 100% by mass relative to 100% by mass of the attachment image.

173. The article having an attachment image according to any one of claims 129 to 142, wherein the total content of the resin and the pigment in the attachment image is 90% to 100% by mass relative to 100% by mass of the attachment image.

174. The article having an attachment image according to any one of claims 129 to 142, wherein the total content of the resin and the pigment in the attachment image is 95% to 100% by mass relative to 100% by mass of the attachment image.

175. The article having an attachment image according to any one of claims 129 to 142, wherein the resin content in the attachment image is from 20% to 95% by mass relative to 100% by mass of the attachment image.

176. The article having an attachment image according to any one of claims 129 to 142, wherein the resin content in the attachment image is 25% to 90% by mass relative to 100% by mass of the attachment image.

177. The article having an attachment image according to any one of claims 129 to 142, wherein the resin content in the attachment image is from 30% to 85% by mass relative to 100% by mass of the attachment image.

178. The article having an attached image according to any one of claims 129 to 142, wherein the thickness of the attached image is 0.1 to 1000 μm.

179. The article having an attached image according to any one of claims 129 to 142, wherein the thickness of the attached image is 0.3 to 500 μm.

180. The article having an attached image according to any one of claims 129 to 142, wherein the thickness of the attached image is 0.5 to 100 μm.

181. The article having an attached image according to any one of claims 129 to 142, wherein the fabric comprises at least one selected from the group consisting of cotton, polyester fibers and polypropylene fibers.

182. The article having an attached image according to any one of claims 129 to 142, wherein the fabric comprises at least one selected from the group consisting of cotton, polyester fibers and polypropylene fibers as a main component.

183. A textile printing method, the textile printing method comprising: Inkjet printing is applied to fabric, where The ink comprises pigments, resin emulsion particles, oxazoline-containing compounds, and an aqueous medium. The resin emulsion particles have an average particle size of 150 nm or more. The resin emulsion particles contain 10% to 20% by mass relative to 100% by mass of the ink. The oxazoline-containing compound is a compound having two or more oxazoline groups in its molecule, and the content of the oxazoline-containing compound is from 0.5% to 10% by mass relative to 100% by mass of the resin emulsion particles. The resin emulsion particles have acidic functional groups, and the resin constituting the resin emulsion particles comprises a polymer obtained by polymerization of monomers containing olefinic unsaturated double bonds.

184. The textile printing method according to claim 183, wherein the pigment comprises a white pigment having an average particle size of 100 to 500 nm.

185. The textile printing method according to claim 183, wherein the pigment comprises a white pigment having an average particle size of 150 to 450 nm.

186. The textile printing method according to claim 183, wherein the pigment comprises a white pigment having an average particle size of 200 to 400 nm.

187. The textile printing method according to claim 183, wherein the pigment comprises a coloring pigment having an average particle size of 20 to 200 nm.

188. The textile printing method according to claim 183, wherein the pigment comprises a coloring pigment having an average particle size of 40 to 150 nm.

189. The textile printing method according to claim 183, wherein the pigment comprises a coloring pigment having an average particle size of 50 to 100 nm.

190. The textile printing method according to claim 183, wherein the average particle size of the resin emulsion particles is 180 nm or more and 330 nm or less.

191. The textile printing method according to claim 183, wherein the average particle size of the resin emulsion particles is greater than 200 nm and less than 300 nm.

192. The textile printing method according to claim 183, wherein the average particle size of the resin emulsion particles is 210 nm or more and 300 nm or less.

193. The textile printing method according to claim 183, wherein the glass transition temperature of the resin emulsion particles is above -50°C and below 0°C.

194. The textile printing method according to claim 183, wherein the glass transition temperature of the resin emulsion particles is above -40°C and below -10°C.

195. The textile printing method according to claim 183, wherein the glass transition temperature of the resin emulsion particles is above -40°C and below -15°C.

196. The textile printing method according to claim 183, wherein the acidic functional group is a carboxyl group.

197. The textile printing method according to claim 183, wherein the acidic functional group includes a carboxyl group.

198. The textile printing method according to claim 196, wherein the content of the acidic functional groups is from 0.06% to 3% by mass relative to 100% by mass of the resin emulsion particles.

199. The textile printing method according to claim 196, wherein the content of the acidic functional group is from 0.1% to 5% by mass relative to 100% by mass of the resin emulsion particles, based on the content of structural units derived from monomers each having the acidic functional group.

200. The textile printing method according to claim 197, wherein the content of the carboxyl group is from 0.06% to 3% by mass relative to 100% by mass of the resin emulsion particles.

201. The textile printing method according to claim 197, wherein the content of the carboxyl group is from 0.1% to 5% by mass relative to 100% by mass of the resin emulsion particles, based on the content of structural units derived from monomers each having the carboxyl group.

202. The textile printing method according to any one of claims 183 to 201, wherein the acid value of the resin emulsion particles is 0.5 to 50 mgKOH / g.

203. The textile printing method according to any one of claims 183 to 201, wherein the acid value of the resin emulsion particles is 0.8 to 40 mgKOH / g.

204. The textile printing method according to any one of claims 183 to 201, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 50,000 or more.

205. The textile printing method according to any one of claims 183 to 201, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 300,000 or more.

206. The textile printing method according to any one of claims 183 to 201, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 550,000 or more.

207. The textile printing method according to any one of claims 183 to 201, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 600,000 or more.

208. The textile printing method according to any one of claims 183 to 201, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 5,000,000 or less.

209. The textile printing method according to any one of claims 183 to 201, wherein the resin emulsion particles have a uniform composition throughout the particles.

210. The textile printing method according to any one of claims 183 to 201, wherein the resin emulsion particles have a core / shell structure consisting of a core and a shell that are different in composition and / or properties.

211. The textile printing method according to any one of claims 183 to 201, wherein the resin emulsion particles are dispersed and stabilized using a surfactant.

212. The textile printing method according to any one of claims 183 to 201, wherein the resin emulsion particles are dispersed and stabilized using a nonionic surfactant or anionic surfactant.

213. The textile printing method according to any one of claims 183 to 201, wherein the resin emulsion particles are dispersed and stabilized using a nonionic surfactant having polymerizable groups or an anionic surfactant having polymerizable groups.

214. The textile printing method according to claim 183, wherein the monomer containing an olefinic unsaturated double bond comprises at least one selected from the group consisting of: Vinyl acetate, vinyl chloride, acrylonitrile, acrylamide, vinyl benzoate, (meth)acrylate, (meth)acrylic acid, styrene, α-methylstyrene, chloromethylstyrene, ethylene, propylene, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, monomethyl maleate, monobutyl maleate, monomethyl itaconic acid, and monobutyl itaconic acid.

215. The textile printing method according to any one of claims 183 to 201, wherein the resin constituting the resin emulsion particles comprises at least one selected from the group consisting of: 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 / vinyl chloride / styrene copolymer, polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / vinyl acetate / (meth)acrylate copolymer, (meth)acrylate copolymer, (meth)acrylate / (meth)acrylate copolymer, (meth)acrylate / styrene copolymer, (meth)acrylate / (meth)acrylate / styrene copolymer, ethylene / vinyl acetate / (meth)acrylate copolymer, (meth)acrylate / urethane copolymer, and acrylonitrile / (meth)acrylate / styrene copolymer.

216. The textile printing method according to any one of claims 183 to 201, wherein the resin emulsion particles comprise an acrylic / styrene polymer.

217. The textile printing method according to claim 216, wherein the acrylic / styrene polymer comprises at least one selected from the group consisting of: (meth)acrylate / styrene copolymer, (meth)acrylate / (meth)acrylate / styrene copolymer and acrylonitrile / (meth)acrylate / styrene copolymer.

218. The textile printing method according to claim 216, wherein the acrylic / styrene polymer comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 50% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer.

219. The textile printing method according to claim 216, wherein the acrylic / styrene polymer comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 80% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer.

220. The textile printing method according to claim 216, wherein the acrylic / styrene polymer comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 95% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer.

221. The textile printing method according to any one of claims 218-220, wherein the content of the styrene monomer in the monomer used to form the acrylic / styrene polymer is from 1% to 55% by mass relative to the total content of the (meth)acrylic monomer and the styrene monomer, which is 100% by mass.

222. The textile printing method according to any one of claims 218-220, wherein the content of the styrene monomer in the monomer used to form the acrylic / styrene polymer is from 5% to 50% by mass relative to the total content of the (meth)acrylic monomer and the styrene monomer, which is 100% by mass.

223. The textile printing method according to any one of claims 218-220, wherein the content of the styrene monomer in the monomer used to form the acrylic / styrene polymer is from 10% to 45% by mass relative to the total content of the (meth)acrylic monomer and the styrene monomer, which is 100% by mass.

224. The textile printing method according to claim 216, wherein the acrylic / styrene polymer comprises a polymer having a carboxyl group.

225. The textile printing method according to claim 224, wherein the content of the carboxyl groups in the acrylic / styrene polymer is from 0.06% to 3% by mass relative to 100% by mass of the resin emulsion particles.

226. The textile printing method according to claim 224 or 225, wherein the content of the carboxyl group in the acrylic / styrene polymer is from 0.1% to 5% by mass relative to 100% by mass of the resin emulsion particles, based on the content of structural units derived from monomers having carboxyl groups.

227. The textile printing method according to claim 216, wherein the structural units derived from (meth)acrylic monomers constituting the acrylic / styrene polymer comprise one or more structural units derived from (meth)acrylic acid.

228. The textile printing method according to claim 216, wherein the structural units derived from (meth)acrylic monomers constituting the acrylic / styrene polymer comprise one or more structural units derived from (meth)acrylates and one or more structural units derived from (meth)acrylic acid.

229. The textile printing method according to claim 228, wherein the (meth)acrylate comprises 2-ethylhexyl acrylate and / or hydroxyethyl methacrylate.

230. The textile printing method according to claim 216, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer is from 0.1% to 5% by mass relative to the total content of 100% by mass of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers.

231. The textile printing method according to claim 216, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer is from 0.2% to 4% by mass relative to the total content of 100% by mass of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers.

232. The textile printing method according to claim 216, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer is from 1% to 3% by mass relative to the total content of 100% by mass of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers.

233. The textile printing method according to any one of claims 183 to 201, wherein the oxazoline-containing compound comprises a water-soluble oxazoline-containing compound.

234. The textile printing method according to any one of claims 183 to 201, wherein the oxazoline-containing compound comprises a water-soluble oxazoline-containing polymer or an emulsion-type oxazoline-containing polymer.

235. The textile printing method according to any one of claims 183 to 201, wherein the oxazoline-containing compound comprises a water-soluble oxazoline-containing polymer.

236. The textile printing method according to any one of claims 183 to 201, wherein the oxazoline-containing compound comprises an oxazoline-containing polymer.

237. The textile printing method according to any one of claims 183 to 201, wherein the content of the oxazoline-containing compound is from 0.5% to 10% by mass relative to 100% by mass of the resin emulsion particles.

238. The textile printing method according to any one of claims 183 to 201, wherein the content of the oxazoline-containing compound is 0.5% to 5% by mass relative to 100% by mass of the resin emulsion particles.

239. The textile printing method according to any one of claims 183 to 201, wherein the water content in the aqueous medium is from 10% by mass to 100% by mass.

240. The textile printing method according to claim 239, wherein the water content in the aqueous medium is from 25% by mass to 100% by mass.

241. The textile printing method according to claim 239, wherein the water content in the aqueous medium is 60% by mass to 100% by mass.

242. The textile printing method according to claim 239, wherein the water content in the aqueous medium is 90% to 100% by mass.

243. The textile printing method according to any one of claims 183 to 201, wherein the aqueous medium comprises an organic solvent.

244. The textile printing method according to claim 243, wherein the organic solvent comprises at least one selected from the group consisting of: glycols, ethers of monoethylene glycol, ethers of monopropylene glycol, ethers of polyethylene glycol, ethers of poly(propylene glycol), and heterocyclic compounds.

245. The textile printing method according to claim 243, wherein the organic solvent comprises at least one selected from the group consisting of: propylene glycol, glycerol, diethylene glycol, triethylene glycol, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monobutyl ether, polyethylene glycol monobutyl ether in a molar number of 2 to 4 of added EO, and 2-pyrrolidone.

246. The textile printing method according to claim 243, wherein the organic solvent comprises at least one selected from the group consisting of: propylene glycol, triethylene glycol, polyethylene glycol monobutyl ether with an addition molar number of 2 to 4 of EO, and 2-pyrrolidone.

247. The textile printing method according to any one of claims 183 to 201, wherein the content of the resin emulsion particles is from 10.5% to 18% by mass relative to 100% by mass of the inkjet textile printing ink.

248. The textile printing method according to any one of claims 183 to 201, wherein the pigment content is from 1% to 20% by mass relative to 100% by mass of the inkjet textile printing ink.

249. The textile printing method according to any one of claims 183 to 201, wherein the pigment content is from 2% to 18% by mass relative to 100% by mass of the inkjet textile printing ink.

250. The textile printing method according to any one of claims 183 to 201, wherein the content of the aqueous medium is 55% to 89% by mass relative to 100% by mass of the inkjet textile printing ink.

251. The textile printing method according to any one of claims 183 to 201, wherein the content of the aqueous medium is 70% to 85% by mass relative to 100% by mass of the inkjet textile printing ink.

252. The textile printing method according to any one of claims 183 to 201, wherein the content of the pigment is from 10% to 80% by mass relative to the total content of the pigment, the resin emulsion particles and the oxazoline-containing compound, which is 100% by mass.

253. The textile printing method according to any one of claims 183 to 201, wherein the content of the pigment is from 15% to 75% by mass relative to the total content of the pigment, the resin emulsion particles and the oxazoline-containing compound, which is 100% by mass.

254. A method for printing transfer textiles, the method using ink, wherein... The ink comprises pigments, resin emulsion particles, oxazoline-containing compounds, and an aqueous medium. The resin emulsion particles have an average particle size of 150 nm or more. The resin emulsion particles contain 10% to 20% by mass relative to 100% by mass of the ink. The oxazoline-containing compound is a compound having two or more oxazoline groups in its molecule, and the content of the oxazoline-containing compound is from 0.5% to 10% by mass relative to 100% by mass of the resin emulsion particles. The resin emulsion particles have acidic functional groups, and the resin constituting the resin emulsion particles comprises a polymer obtained by polymerizing monomers containing olefinic unsaturated double bonds.

255. The transfer textile printing method according to claim 254, wherein the transfer textile printing method comprises: The transfer paper manufacturing step involves using an inkjet printer to spray ink onto a transfer paper substrate to produce transfer paper with an image formed thereon. A transfer step in which the transfer paper is stacked on the fabric and heated and / or pressed to transfer the image formed on the transfer paper to the fabric; as well as The peeling step involves peeling the transfer paper from the fabric onto which the image has been transferred in the transfer step.

256. The method for printing on textile transfer according to claim 255, wherein in the transfer paper manufacturing step, after the ink is sprayed onto the transfer paper substrate, the sprayed ink is dried to form the image.

257. The transfer textile printing method according to claim 254, wherein the pigment comprises a white pigment having an average particle size of 100 to 500 nm.

258. The transfer textile printing method according to claim 254, wherein the pigment comprises a white pigment having an average particle size of 150 to 450 nm.

259. The transfer textile printing method according to claim 254, wherein the pigment comprises a white pigment having an average particle size of 200 to 400 nm.

260. The transfer textile printing method according to claim 254, wherein the pigment comprises a coloring pigment having an average particle size of 20 to 200 nm.

261. The transfer textile printing method according to claim 254, wherein the pigment comprises a coloring pigment having an average particle size of 40 to 150 nm.

262. The transfer textile printing method according to claim 254, wherein the pigment comprises a coloring pigment having an average particle size of 50 to 100 nm.

263. The transfer textile printing method according to claim 254, wherein the average particle size of the resin emulsion particles is 180 nm or more and 330 nm or less.

264. The transfer textile printing method according to claim 254, wherein the average particle size of the resin emulsion particles is greater than 200 nm and less than 300 nm.

265. The transfer textile printing method according to claim 254, wherein the average particle size of the resin emulsion particles is 210 nm or more and 300 nm or less.

266. The transfer textile printing method according to claim 254, wherein the glass transition temperature of the resin emulsion particles is above -50°C and below 0°C.

267. The transfer textile printing method according to claim 254, wherein the glass transition temperature of the resin emulsion particles is above -40°C and below -10°C.

268. The transfer textile printing method according to claim 254, wherein the glass transition temperature of the resin emulsion particles is above -40°C and below -15°C.

269. The transfer textile printing method according to claim 254, wherein the acidic functional group is a carboxyl group.

270. The transfer textile printing method according to claim 254, wherein the acidic functional group includes a carboxyl group.

271. The method for printing transfer textiles according to claim 269, wherein the content of the acidic functional groups is from 0.06% to 3% by mass relative to 100% by mass of the resin emulsion particles.

272. The transfer textile printing method according to claim 269, wherein the content of the acidic functional group is from 0.1% to 5% by mass relative to 100% by mass of the resin emulsion particles, based on the content of structural units derived from monomers each having the acidic functional group.

273. The method for printing transfer textiles according to claim 270, wherein the content of the carboxyl group is from 0.06% to 3% by mass relative to 100% by mass of the resin emulsion particles.

274. The transfer textile printing method according to claim 270, wherein the content of the carboxyl group is from 0.1% to 5% by mass relative to 100% by mass of the resin emulsion particles, based on the content of structural units derived from monomers each having the carboxyl group.

275. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the acid value of the resin emulsion particles is 0.5 to 50 mgKOH / g.

276. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the acid value of the resin emulsion particles is 0.8 to 40 mgKOH / g.

277. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 50,000 or more.

278. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 300,000 or more.

279. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 550,000 or more.

280. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 600,000 or more.

281. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the weight-average molecular weight of the resin component constituting the resin emulsion particles is 5,000,000 or less.

282. The transfer textile printing method according to any one of claims 254 to 274, wherein the resin emulsion particles have a uniform composition throughout the particles.

283. The transfer textile printing method according to any one of claims 254 to 274, wherein the resin emulsion particles have a core / shell structure consisting of a core and a shell that are different in composition and / or properties.

284. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the resin emulsion particles are dispersed and stabilized using a surfactant.

285. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the resin emulsion particles are dispersed and stabilized using a nonionic surfactant or anionic surfactant.

286. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the resin emulsion particles are dispersed and stabilized using a nonionic surfactant having polymerizable groups or an anionic surfactant having polymerizable groups.

287. The transfer textile printing method according to claim 254, wherein the monomer containing an olefinic unsaturated double bond comprises at least one selected from the group consisting of: Vinyl acetate, vinyl chloride, acrylonitrile, acrylamide, vinyl benzoate, (meth)acrylate, (meth)acrylic acid, styrene, α-methylstyrene, chloromethylstyrene, ethylene, propylene, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, monomethyl maleate, monobutyl maleate, monomethyl itaconic acid, and monobutyl itaconic acid.

288. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the resin constituting the resin emulsion particles comprises at least one selected from the group consisting of: 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 / vinyl chloride / styrene copolymer, polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / vinyl acetate / (meth)acrylate copolymer, (meth)acrylate copolymer, (meth)acrylate / (meth)acrylate copolymer, (meth)acrylate / styrene copolymer, (meth)acrylate / (meth)acrylate / styrene copolymer, ethylene / vinyl acetate / (meth)acrylate copolymer, (meth)acrylate / urethane copolymer, and acrylonitrile / (meth)acrylate / styrene copolymer.

289. The transfer textile printing method according to any one of claims 254 to 274, wherein the resin emulsion particles comprise an acrylic / styrene polymer.

290. The transfer textile printing method according to claim 289, wherein the acrylic / styrene polymer comprises at least one selected from the group consisting of: (meth)acrylate / styrene copolymer, (meth)acrylate / (meth)acrylate / styrene copolymer and acrylonitrile / (meth)acrylate / styrene copolymer.

291. The method for printing transfer textiles according to claim 289, wherein the acrylic / styrene polymer comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 50% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer.

292. The method for printing transfer textiles according to claim 289, wherein the acrylic / styrene polymer comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 80% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer.

293. The transfer textile printing method according to claim 289, wherein the acrylic / styrene polymer comprises structural units derived from (meth)acrylic monomers and structural units derived from styrene monomers, and the total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene monomers is 95% by mass or more relative to a total of 100% by mass of all structural units constituting the acrylic / styrene polymer.

294. The transfer textile printing method according to any one of claims 291-293, wherein the content of the styrene monomer in the monomer used to form the acrylic / styrene polymer is from 1% to 55% by mass relative to the total content of the (meth)acrylic monomer and the styrene monomer, which is 100% by mass.

295. The transfer textile printing method according to any one of claims 291-293, wherein the content of the styrene monomer in the monomer used to form the acrylic / styrene polymer is from 5% to 50% by mass relative to the total content of the (meth)acrylic monomer and the styrene monomer, which is 100% by mass.

296. The transfer textile printing method according to any one of claims 291-293, wherein the content of the styrene monomer in the monomer used to form the acrylic / styrene polymer is from 10% to 45% by mass relative to the total content of the (meth)acrylic monomer and the styrene monomer, which is 100% by mass.

297. The transfer textile printing method according to claim 289, wherein the acrylic / styrene polymer comprises a polymer having a carboxyl group.

298. The transfer textile printing method according to claim 297, wherein the content of the carboxyl groups in the acrylic / styrene polymer is from 0.06% to 3% by mass relative to 100% by mass of the resin emulsion particles.

299. The transfer textile printing method according to claim 297 or 298, wherein the content of the carboxyl group in the acrylic / styrene polymer is from 0.1% to 5% by mass relative to 100% by mass of the resin emulsion particles, based on the content of structural units derived from monomers having carboxyl groups.

300. The transfer textile printing method according to claim 289, wherein the structural units derived from (meth)acrylic monomers constituting the acrylic / styrene polymer comprise one or more structural units derived from (meth)acrylic acid.

301. The method for printing transfer textiles according to claim 289, wherein the structural units derived from (meth)acrylic monomers constituting the acrylic / styrene polymer comprise one or more structural units derived from (meth)acrylates and one or more structural units derived from (meth)acrylic acid.

302. The transfer textile printing method according to claim 301, wherein the (meth)acrylate comprises 2-ethylhexyl acrylate and / or hydroxyethyl methacrylate.

303. The transfer textile printing method according to claim 289, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer is from 0.1% to 5% by mass relative to the total content of 100% by mass of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers.

304. The method for printing transfer textiles according to claim 289, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer is from 0.2% to 4% by mass relative to the total content of 100% by mass of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers.

305. The method for printing transfer textiles according to claim 289, wherein the content of the structural units derived from (meth)acrylic acid in the acrylic / styrene polymer is from 1% to 3% by mass relative to the total content of 100% by mass of the structural units derived from (meth)acrylic acid monomers and the structural units derived from styrene monomers.

306. The transfer textile printing method according to any one of claims 254 to 274, wherein the oxazoline-containing compound comprises a water-soluble oxazoline-containing compound.

307. The transfer textile printing method according to any one of claims 254 to 274, wherein the oxazoline-containing compound comprises a water-soluble oxazoline-containing polymer or an emulsion-type oxazoline-containing polymer.

308. The transfer textile printing method according to any one of claims 254 to 274, wherein the oxazoline-containing compound comprises a water-soluble oxazoline-containing polymer.

309. The transfer textile printing method according to any one of claims 254 to 274, wherein the oxazoline-containing compound comprises an oxazoline-containing polymer.

310. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the content of the oxazoline-containing compound is from 0.5% to 10% by mass relative to 100% by mass of the resin emulsion particles.

311. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the content of the oxazoline-containing compound is 0.5% to 5% by mass relative to 100% by mass of the resin emulsion particles.

312. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the water content in the aqueous medium is from 10% by mass to 100% by mass.

313. The transfer textile printing method according to claim 312, wherein the water content in the aqueous medium is from 25% to 100% by mass.

314. The transfer textile printing method according to claim 312, wherein the water content in the aqueous medium is 60% to 100% by mass.

315. The transfer textile printing method according to claim 312, wherein the water content in the aqueous medium is 90% to 100% by mass.

316. The transfer textile printing method according to any one of claims 254 to 274, wherein the aqueous medium comprises an organic solvent.

317. The method for printing transfer textiles according to claim 316, wherein the organic solvent comprises at least one selected from the group consisting of: glycols, ethers of monoethylene glycol, ethers of monopropylene glycol, ethers of polyethylene glycol, ethers of poly(propylene glycol), and heterocyclic compounds.

318. The method for printing transfer textiles according to claim 316, wherein the organic solvent comprises at least one selected from the group consisting of: propylene glycol, glycerol, diethylene glycol, triethylene glycol, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monobutyl ether, polyethylene glycol monobutyl ether in a molar number of 2 to 4 of added EO, and 2-pyrrolidone.

319. The transfer textile printing method according to claim 316, wherein the organic solvent comprises at least one selected from the group consisting of: propylene glycol, triethylene glycol, polyethylene glycol monobutyl ether with an addition molar number of 2 to 4 of EO, and 2-pyrrolidone.

320. The transfer textile printing method according to any one of claims 254 to 274, wherein the content of the resin emulsion particles is 10.5% to 18% by mass relative to 100% by mass of the ink.

321. The transfer textile printing method according to any one of claims 254 to 274, wherein the pigment content is 1% to 20% by mass relative to 100% by mass of the ink.

322. The transfer textile printing method according to any one of claims 254 to 274, wherein the pigment content is 2% to 18% by mass relative to 100% by mass of the ink.

323. The transfer textile printing method according to any one of claims 254 to 274, wherein the content of the aqueous medium is 55% to 89% by mass relative to 100% by mass of the ink.

324. The method for printing transfer textiles according to any one of claims 254 to 274, wherein the content of the aqueous medium is 70% to 85% by mass relative to 100% by mass of the ink.

325. The transfer textile printing method according to any one of claims 254 to 274, wherein the pigment content is from 10% to 80% by mass relative to the total content of the pigment, the resin emulsion particles and the oxazoline-containing compound, which is 100% by mass.

326. The transfer textile printing method according to any one of claims 254 to 274, wherein the pigment content is 15% to 75% by mass relative to the total content of the pigment, the resin emulsion particles and the oxazoline-containing compound, which is 100% by mass.

Images