Pretreatment liquid for inkjet textile printing

Abstract

The present invention addresses the problem of providing a pretreatment liquid for inkjet textile printing that has excellent storage stability and that makes it possible to obtain a printed product which has an excellent color forming property and excellent wet rubbing fastness.　A pretreatment liquid for inkjet textile printing according to the present invention is characterized by containing a water-soluble multivalent metal salt, resin emulsion particles, an oxazoline group-containing compound, and an aqueous medium, wherein: the resin emulsion particles contains a nonionic emulsifier; and a resin that constitutes the resin emulsion particles contains, in an amount of 0.1-2 mass%, a structural unit which has a carboxy group (A) and / or a salt thereof.

Description

Pretreatment liquid for inkjet printing

[0001] The present invention relates to a pretreatment liquid for ink-jet textile printing.

[0002] Textile printing methods for recording images on fabrics such as cloth and textile products have been known for some time. Screen printing and the like have been widely used as textile printing methods, but in recent years, inkjet printing has also become popular from the viewpoint of efficient use of ink used in textile printing. In textile printing using the inkjet method (hereinafter referred to as "inkjet printing"), ink for inkjet printing is ejected from the nozzles of an inkjet head and deposited on the fabric, thereby recording an image on the fabric.

[0003] In such inkjet textile printing, a method is known in which a fabric is treated with a pretreatment liquid containing a flocculant, and then ink is deposited on the treated surface of the fabric to flocculate components such as pigments contained in the ink, thereby enhancing the color development of the image in the resulting printed product (fabric on which an image is recorded).

[0004] For example, Patent Document 1 discloses a pretreatment agent containing a metal salt, an aqueous polymer substantially free of carboxyl groups, and a crosslinking agent capable of crosslinking with carboxyl groups contained in components contained in the ink. However, Patent Document 1, which uses an aqueous polymer substantially free of carboxyl groups, may not have sufficient wet rub fastness. On the other hand, Patent Document 2 discloses a pretreatment liquid for inkjet printing, which is characterized by containing an acrylic copolymer (A) having carboxyl groups, a cationic water-soluble resin (B), and a resin (C) having an oxazoline group. However, Patent Document 2, which uses a cationic water-soluble resin as a flocculant, may not have sufficient coagulation power, and therefore may have insufficient color development.

[0005] JP 2019-183126 A Patent No. 4099727

[0006] Therefore, there is a need for a pretreatment liquid capable of producing printed textiles that are excellent in wet rub fastness and color development. However, it has been found that when the cationic water-soluble resin in the pretreatment liquid of Patent Document 2 is replaced with a metal salt with strong coagulation power in order to enhance color development, the pretreatment liquid aggregates, resulting in a pretreatment liquid with poor storage stability. Therefore, an object of the present invention is to provide a pretreatment liquid for inkjet printing that is excellent in storage stability and that can produce printed textiles that are excellent in color development and wet rub fastness.

[0007] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that a pretreatment liquid containing a water-soluble polyvalent metal salt, resin emulsion particles having a predetermined amount of structural units containing a carboxy group and / or a salt thereof and containing a nonionic emulsifier, an oxazoline group-containing compound, and an aqueous medium has good storage stability, and that by treating a fabric in advance with this pretreatment liquid in inkjet textile printing, the color development and wet rub fastness of the resulting printed textile can be improved, thereby completing the present invention.

[0008] That is, the present invention is as follows. [1] A pretreatment liquid for inkjet printing, comprising a water-soluble polyvalent metal salt, resin emulsion particles, an oxazoline group-containing compound, and an aqueous medium, wherein the resin emulsion particles contain a nonionic emulsifier, and a resin constituting the resin emulsion particles contains a structural unit having a carboxy group and / or a salt thereof, and the content of the structural unit having a carboxy group and / or a salt thereof is 0.1 to 2 mass% in the resin. [2] The pretreatment liquid for inkjet printing according to [1], wherein the nonionic emulsifier is a reactive emulsifier. [3] The pretreatment liquid for inkjet printing according to [1] or [2], wherein the resin constituting the resin emulsion particles contains a structural unit derived from an internally crosslinkable monomer. [4] The pretreatment liquid for inkjet printing according to any one of [1] to [3], wherein the aqueous medium contains water and a water-soluble organic solvent, and the water-soluble organic solvent contains a glycol. [5] The inkjet printing pretreatment liquid according to any one of [1] to [4], wherein the resin constituting the resin emulsion particles contains a structural unit derived from a styrene-based monomer. [6] The inkjet printing pretreatment liquid according to any one of [1] to [5], wherein the water-soluble polyvalent metal salt is an alkaline earth metal salt. [7] The inkjet printing pretreatment liquid according to any one of [1] to [6], wherein the anion constituting the water-soluble polyvalent metal salt is a chloride ion. [8] The inkjet printing pretreatment liquid according to any one of [1] to [7], wherein the water-soluble polyvalent metal salt has a calcium nitrate content of 50% by mass or less. [9] The inkjet printing pretreatment liquid according to any one of [1] to [8], wherein the resin constituting the resin emulsion particles contains a structural unit derived from a hydroxyl group-containing (meth)acrylic acid ester.

[10] The inkjet printing pretreatment liquid according to any one of [1] to [9], wherein the resin constituting the resin emulsion particles contains a structural unit having a carboxy group and / or a salt thereof; a structural unit derived from a (meth)acrylic acid alkyl ester having a homopolymer glass transition temperature of 0°C or lower; a structural unit derived from a (meth)acrylic acid alkyl ester and / or a structural unit derived from a styrene-based monomer having a homopolymer glass transition temperature of above 0°C; and a structural unit derived from a hydroxyl group-containing (meth)acrylic acid ester.

[11] The inkjet printing pretreatment liquid according to any one of [1] to

[10] , wherein the resin constituting the resin emulsion particles has a glass transition temperature of -50 to 10°C.

[12] The inkjet printing pretreatment liquid according to any one of [1] to

[11] , wherein the aqueous medium contains water and a water-soluble organic solvent, and the water-soluble organic solvent has a boiling point of 150°C or higher.

[13] A fabric to which the pretreatment liquid according to any one of [1] to

[12] has been applied.

[14] A printed item comprising a fabric having a surface to which the solid content of the pretreatment liquid according to any one of [1] to

[12] adhered, and an ink adhered to the solid content.

[15] A method for treating a fabric with the pretreatment liquid according to any one of [1] to

[12] , and then performing inkjet printing.

[16] A method for producing a printed item, comprising: a pretreatment step of adhering the pretreatment liquid according to any one of [1] to

[12] to a fabric; and an image formation step of adhering ink by an inkjet method to the treated surface of the fabric obtained in the pretreatment step to form an image.

[0009] According to the present invention, it is possible to provide a pretreatment liquid for ink-jet printing that is excellent in storage stability and that can give printed products that are excellent in color development and wet rub fastness.

[0010] One embodiment of the present invention will be described below, but the present invention is not limited thereto. In this specification, unless otherwise specified, "A to B" representing a numerical range means "A or more and B or less." Furthermore, "(meth)acrylic acid" means acrylic acid or methacrylic acid, and "(meth)acrylate" means acrylate or methacrylate. The same applies to terms such as "(meth)acryloxy" and "(meth)acryloyl."

[0011] [Pretreatment Liquid for Inkjet Textile Printing] The pretreatment liquid for inkjet textile printing of the present invention (hereinafter sometimes simply referred to as the "pretreatment liquid") is a pretreatment liquid containing a water-soluble polyvalent metal salt, resin emulsion particles, an oxazoline group-containing compound, and an aqueous medium, wherein the resin emulsion particles contain a nonionic emulsifier, the resin constituting the resin emulsion particles contains a structural unit having a carboxy group and / or a salt thereof, and the content of the structural unit having a carboxy group and / or a salt thereof is 0.1 to 2 mass% in the resin. In inkjet textile printing, pretreatment of a fabric with the pretreatment liquid of the present invention improves the color development and wet rub fastness of the resulting printed textile, and preferably also improves the texture. Furthermore, the pretreatment liquid of the present invention suppresses aggregation even after long-term storage, i.e., has excellent storage stability. Below, each component contained in the pretreatment liquid of the present invention is described.

[0012] [Water-soluble polyvalent metal salt] The water-soluble polyvalent metal salt reacts with components such as pigments contained in the inkjet printing ink described below, thereby causing the components to aggregate, thereby improving the color development of images formed with the ink in inkjet printing.

[0013] The water-soluble polyvalent metal salt is preferably a compound composed of a divalent or higher metal ion and an anion, and is a compound that dissolves 1 g or more in 100 mL of water at 25°C.

[0014] Examples of metals constituting the divalent or higher metal ions include alkaline earth metals such as magnesium, calcium, strontium, and barium; and transition metals (preferably fourth-period transition metals) such as titanium, chromium, copper, and zinc. Of these, alkaline earth metals are preferred, and calcium is more preferred, from the viewpoint of excellent coagulation properties for pigments and the like. Examples of the anions include halide ions such as chloride ions, bromide ions, and iodide ions, nitrate ions, sulfate ions, acetate ions, carbonate ions, and hydroxide ions. Of these, chloride ions and sulfate ions are preferred, and chloride ions are more preferred from the viewpoint of suppressing yellowing of printed textiles.

[0015] Specific examples of the water-soluble polyvalent metal salt include alkaline earth metal salts such as calcium salts (calcium chloride, calcium nitrate, calcium acetate, etc.), magnesium salts (magnesium chloride, magnesium acetate, magnesium sulfate, etc.), and barium salts (barium chloride, etc.); and transition metal salts such as zinc salts (zinc chloride, zinc sulfate, etc.) and copper salts (copper nitrate, etc.). Among these, alkaline earth metal salts are preferred, calcium salts are more preferred, calcium chloride and calcium nitrate are even more preferred, and calcium chloride is particularly preferred. These water-soluble polyvalent metal salts may be used alone or in combination of two or more. The content of calcium chloride in the water-soluble polyvalent metal salt is preferably more than 50% by mass, more preferably more than 70% by mass, even more preferably more than 90% by mass, and particularly preferably 100% by mass.

[0016] The content of the water-soluble polyvalent metal salt is preferably 50 to 5,000 parts by mass, more preferably 60 to 1,500 parts by mass, still more preferably 80 to 500 parts by mass, and particularly preferably 100 to 300 parts by mass, relative to 100 parts by mass of the resin emulsion particles. By setting the content of the water-soluble polyvalent metal salt to a predetermined value or more, the color developability of the printed textile can be further improved, and by setting the content of the water-soluble polyvalent metal salt to a predetermined value or less, the wet rub fastness of the printed textile can be further improved.

[0017] When the water-soluble polyvalent metal salt is contained in an amount of 50 parts by mass or more per 100 parts by mass of resin emulsion particles (particularly when an alkaline earth metal salt such as a calcium salt is contained as the water-soluble polyvalent metal salt), the content of calcium salts other than calcium chloride (hereinafter referred to as other calcium salts, particularly calcium nitrate) is preferably low, from the viewpoints of suppressing yellowing of the obtained printed textile and further improving the storage stability of the pretreatment liquid. The content of other calcium salts in the water-soluble polyvalent metal salt is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 10% by mass or less, and it is particularly preferred that the water-soluble polyvalent metal salt does not contain other calcium salts.

[0018] [Resin emulsion particles] The shape of the resin emulsion particles is not particularly limited, but is usually spherical. The shape of the resin emulsion particles can be measured using a transmission electron microscope or a scanning electron microscope. The resin emulsion particles may have a single-layer structure or a multi-layer structure (e.g., a core-shell structure).

[0019] The average particle size of the resin emulsion particles is not particularly limited, but is preferably 50 to 500 nm, more preferably 100 to 400 nm, and even more preferably 150 to 350 nm. By adjusting the average particle size of the resin emulsion particles to fall within the above range, it becomes easier to incorporate the resin emulsion particles at a high concentration while maintaining the viscosity of the pretreatment liquid within an appropriate range. The average particle size of the resin emulsion particles may be determined by the cumulant average particle size measured by dynamic light scattering, as shown in the examples described below.

[0020] (A) Structural unit having a carboxy group and / or a salt thereof The resin constituting the resin emulsion particles contains a structural unit having a carboxy group and / or a salt thereof (hereinafter, sometimes referred to as a structural unit having a carboxy group and / or a salt thereof (A)). When the resin contains a structural unit having a carboxy group and / or a salt thereof (A), a crosslinked structure can be formed between resin emulsion particles, etc., by an oxazoline group-containing compound described below. Furthermore, the interaction between the fabric and the pretreatment liquid is enhanced, which may improve the wet rub fastness of the resulting printed textile. Furthermore, when the resin contains a structural unit having a carboxy group and / or a salt thereof (A), the color development of the resulting printed textile tends to be further improved.

[0021] In this specification, the term "structural unit having a carboxy group and / or a salt thereof" refers to a structural unit derived from a monomer and is not particularly limited as long as the structural unit has a carboxy group and / or a salt thereof. That is, it may be a structural unit obtained by polymerizing a monomer having a carboxy group and / or a salt thereof (i.e., a structural unit derived from a monomer having a carboxy group and / or a salt thereof), or a structural unit formed by modifying a structural unit obtained by polymerizing a specific monomer so that it has a carboxy group and / or a salt thereof.

[0022] Examples of the salt of the carboxy group include alkali metal salts of the carboxy group, alkaline earth metal salts of the carboxy group, and ammonium salts of the carboxy group. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include magnesium, calcium, and barium. Examples of the ammonium include NH4 + and organic ammonium (for example, tetraalkylammonium such as tetramethylammonium and tetrabutylammonium, trialkylammonium such as trimethylammonium, triethylammonium and tributylammonium, cycloalkylammonium such as cyclohexylammonium, and hydroxyalkylammonium such as diethanolammonium and triethanolammonium), among which NH4 + , Tetra C 1-10 Alkylammonium, TriC 1-10 The salt of the carboxy group is preferably an alkali metal salt of the carboxy group or an ammonium salt of the carboxy group, more preferably an ammonium salt of the carboxy group, and more preferably an NH4 + Salt is more preferred.

[0023] As described above, (A) the structural unit having a carboxy group and / or a salt thereof may be a structural unit obtained by polymerizing a monomer having a carboxy group and / or a salt thereof (i.e., a structural unit derived from a monomer having a carboxy group and / or a salt thereof).

[0024] The monomer having a carboxy group and / or a salt thereof may be any monomer having at least one carboxy group and / or a salt thereof and at least one polymerizable unsaturated group in the molecule. Specific examples of the monomer having a carboxy group (hereinafter sometimes referred to as (A1) monomer having a carboxy group) include carboxylic acid compounds such as unsaturated monocarboxylic acids such as (meth)acrylic acid, cinnamic acid, and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; monoesters of unsaturated dicarboxylic acids such as maleic acid monomethyl ester, maleic acid monobutyl ester, itaconic acid monomethyl ester, and itaconic acid monobutyl ester; anhydrides of unsaturated dicarboxylic acids such as maleic anhydride; 2-(meth)acryloyloxyethyl succinic acid; 2-(meth)acryloyloxyethyl phthalic acid; and 2-(meth)acryloyloxyethyl hexahydrophthalic acid. Specific examples of the monomer having a carboxyl group salt (hereinafter sometimes referred to as (A2) monomer having a carboxyl group salt) include alkali metal salts of the above-mentioned carboxylic acid compounds, alkaline earth metal salts of the above-mentioned carboxylic acid compounds, and ammonium salts of the above-mentioned carboxylic acid compounds. Specific examples of the alkali metals, alkaline earth metals, and ammonium constituting the (A2) monomer having a carboxyl group salt are the same as the alkali metals, alkaline earth metals, and ammonium described above, and preferred embodiments thereof are also the same. The monomer having a carboxyl group and / or a salt thereof is preferably an unsaturated monocarboxylic acid and / or a salt thereof, more preferably (meth)acrylic acid and / or a salt thereof, and even more preferably acrylic acid and / or a salt thereof.

[0025] As described above, the structural unit (A) having a carboxy group and / or a salt thereof may be a structural unit into which a carboxy group and / or a salt thereof has been introduced by modifying (e.g., neutralization, hydrolysis, etc.) a structure obtained by polymerizing a predetermined monomer (hereinafter, sometimes referred to as a predetermined monomer (A3)). (For example, a structural unit having the same structure as a structural unit derived from a monomer having a carboxy group and / or a salt thereof by modification after polymerization.) The method of modification is not particularly limited. For example, when a monomer having a carboxy group (A1) is used as the predetermined monomer (A3), the structural unit derived from the monomer having a carboxy group (A1) can be modified into a structural unit having a salt of a carboxy group by polymerizing the monomer having a carboxy group and then neutralizing it by adding a basic substance (e.g., alkali metal hydroxide, alkaline earth metal hydroxide, amine, ammonia, etc.). Furthermore, an ester of the carboxylic acid compound (e.g., C of the carboxylic acid compound) can be used as the predetermined monomer (A3). 1-4 In the case where a structural unit derived from the ester of a carboxylic acid compound (e.g., alkyl ester) is used, the structural unit derived from the ester of a carboxylic acid compound can be modified into a structural unit having a carboxy group by polymerizing the ester of the carboxylic acid compound and then hydrolyzing the ester.

[0026] The (A) structural unit having a carboxy group and / or a salt thereof is preferably a structural unit derived from an unsaturated monocarboxylic acid, a structural unit derived from a salt of an unsaturated monocarboxylic acid (preferably an ammonium salt of an unsaturated monocarboxylic acid), or a structural unit having a salt of a carboxy group (preferably an ammonium salt of a carboxy group) formed by neutralizing a structural unit derived from an unsaturated monocarboxylic acid; more preferably a structural unit derived from (meth)acrylic acid, a salt of (meth)acrylic acid (preferably an ammonium salt of (meth)acrylic acid), or a structural unit having a salt of a carboxy group (preferably an ammonium salt of a carboxy group) formed by neutralizing a structural unit derived from (meth)acrylic acid; and even more preferably a structural unit derived from acrylic acid, a salt of acrylic acid (preferably an ammonium salt of acrylic acid), or a structural unit having a salt of a carboxy group (preferably an ammonium salt of a carboxy group) formed by neutralizing a structural unit derived from acrylic acid.

[0027] In particular, from the viewpoint of achieving more excellent storage stability, the resin constituting the resin emulsion particles preferably contains a structural unit having a salt of a carboxy group. In a total of 100 mol % of the carboxy groups and the salts of the carboxy groups contained in the resin constituting the resin emulsion particles, the proportion of the salt of the carboxy group is, for example, 30 mol % or more, preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 90 mol % or more, and may even be 100 mol %.

[0028] The structural unit (A) having a carboxy group and / or a salt thereof may be contained in the resin either alone or in combination of two or more kinds.

[0029] The content of (A) structural units having a carboxy group and / or a salt thereof in the resin is 0.1 to 2% by mass. By setting the content of (A) structural units having a carboxy group and / or a salt thereof to 0.1% by mass or more, crosslinking with the oxazoline group-containing compound proceeds sufficiently, thereby improving wet rub fastness. Furthermore, by setting the content to 2% by mass or less and appropriately suppressing the amount of hydrophilic carboxy groups and / or salts thereof, wet rub fastness is improved, and further, aggregation of the resin emulsion particles and the water-soluble polyvalent metal salt is suppressed, thereby improving storage stability. The content is preferably 0.2 to 1.5% by mass, more preferably 0.3 to 1.0% by mass.

[0030] (B) Structural Unit Derived from (Meth)acrylic Acid Alkyl Ester The resin may further contain (B) a structural unit derived from a (meth)acrylic acid alkyl ester. The (meth)acrylic acid alkyl ester is an ester of (meth)acrylic acid and an alkyl alcohol, and the alkyl group constituting the alkyl alcohol may be chain-like (specifically, linear or branched) or cyclic. Hereinafter, a (meth)acrylic acid alkyl ester in which the alkyl group constituting the alkyl alcohol is chain-like will be referred to as a (meth)acrylic acid chain-like alkyl ester, and a (meth)acrylic acid alkyl ester in which the alkyl group constituting the alkyl alcohol is cyclic will be referred to as a (meth)acrylic acid cyclic alkyl ester.

[0031] Specific examples of the (meth)acrylic acid chain alkyl ester include esters of (meth)acrylic acid and chain alkyl alcohols having 1 to 30 carbon atoms, 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, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, tridecyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, heneicosyl (meth)acrylate, and tetracosyl (meth)acrylate. The chain alkyl alcohol having 1 to 30 carbon atoms may be any of primary, secondary, and tertiary alcohols, with primary alcohols being preferred. The primary alcohol may be linear or branched, with branched alcohols being preferred.

[0032] Specific examples of (meth)acrylic acid cyclic alkyl esters include (meth)acrylic acid cycloalkyl esters such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, and cyclooctyl (meth)acrylate; (meth)acrylic acid esters having a bicyclic saturated hydrocarbon ring such as bornyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; and (meth)acrylic acid esters having three or more saturated hydrocarbon rings such as 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate. Among these, (meth)acrylic acid cycloalkyl esters are preferred, and (meth)acrylic acid C 6-10 Cycloalkyl esters are more preferred, and methacrylic acid C 6-10 Cycloalkyl esters are more preferred, with cyclohexyl methacrylate being especially preferred.

[0033] The structural unit (B) derived from a (meth)acrylic acid alkyl ester may be contained in the resin either alone or in combination of two or more.

[0034] The (B) (meth)acrylic acid alkyl ester is preferably a (meth)acrylic acid alkyl ester whose homopolymer has a glass transition temperature (Tg) of 0° C. or lower (hereinafter, may be referred to as a (B1) low-Tg (meth)acrylic acid alkyl ester). When the resin contains a structural unit derived from the (B1) low-Tg (meth)acrylic acid alkyl ester, the obtained printed textile tends to have excellent texture.

[0035] The Tg of the (B1) low Tg (meth)acrylic acid alkyl ester is preferably from -100 to -20°C, more preferably from -80 to -30°C.

[0036] The (B1) low-Tg (meth)acrylic acid alkyl ester is preferably a low-Tg chain (meth)acrylic acid alkyl ester, and examples thereof include linear acrylic acid alkyl esters such as ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, and n-nonyl acrylate; branched acrylic acid alkyl esters such as isobutyl acrylate, 2-ethylhexyl acrylate, and isononyl acrylate; and the like. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are preferred, and 2-ethylhexyl acrylate is more preferred. In cases where the copolymer contains both structural units derived from a linear acrylate alkyl ester such as n-butyl acrylate and structural units derived from a branched acrylate alkyl ester such as 2-ethylhexyl acrylate, the content of the structural units derived from the branched acrylate alkyl ester is, for example, 20% by mass or more, preferably 50% by mass or more, and more preferably 80% by mass or more, relative to 100% by mass of the structural units derived from the low Tg (meth)acrylate alkyl ester (B1). The upper limit may be 100% by mass or may be 95% by mass.

[0037] The content of the structural units derived from (B1) low Tg alkyl (meth)acrylate in the resin is preferably 10 to 90% by mass, more preferably 30 to 80% by mass, and even more preferably 40 to 70% by mass. The content of the structural units derived from (B1) low Tg alkyl (meth)acrylate is, for example, 20 to 300 parts by mass, preferably 30 to 200 parts by mass, and more preferably 40 to 150 parts by mass per part by mass of the structural units (A) having a carboxy group and / or a salt thereof.

[0038] On the other hand, when the (meth)acrylic acid alkyl ester contains structural units derived from a monomer whose homopolymer has a higher Tg than the (B1) low-Tg (meth)acrylic acid alkyl ester (i.e., a (meth)acrylic acid alkyl ester whose homopolymer has a Tg of above 0°C, hereinafter referred to as the (B2) high-Tg (meth)acrylic acid alkyl ester), it is preferable to adjust the content of the structural units derived from the (B2) high-Tg chain (meth)acrylic acid alkyl ester together with the structural units derived from the (C) styrene-based monomer described below. Adjusting the content of the structural units derived from (B1) and the structural units derived from (B2) and / or (C) makes it easy to adjust the Tg of the resin emulsion particles.

[0039] Examples of (B2) high Tg (meth)acrylic acid alkyl esters include linear (meth)acrylic acid alkyl esters having a homopolymer Tg of above 0° C., such as methyl (meth)acrylate, ethyl methacrylate, and tert-butyl (meth)acrylate, and cyclic (meth)acrylic acid alkyl esters having a homopolymer Tg of above 0° C., such as cyclohexyl methacrylate and isobornyl acrylate. The Tg of the homopolymer of (B2) high Tg (meth)acrylic acid alkyl ester is preferably 30 to 120° C., and more preferably 50 to 110° C.

[0040] (C) Structural unit derived from styrene-based monomer The resin constituting the resin emulsion particles preferably further contains (C) a structural unit derived from a styrene-based monomer. When the resin contains (C) a structural unit derived from a styrene-based monomer, the wet rub fastness and color development of the obtained printed textile are further improved.

[0041] The styrene-based monomer (C) may be a C styrene-based monomer containing a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a tert-butyl group). 1-4 styrene which may have one or more substituents such as alkyl groups;

[0042] Specific examples of the styrene-based monomer (C) include styrene, α-methylstyrene, p-methylstyrene, tert-butylstyrene, chlorostyrene, and chloromethylstyrene, with styrene being preferred.

[0043] The structural unit (C) derived from a styrene-based monomer may be contained in the resin alone or in combination of two or more kinds.

[0044] The content of the structural unit derived from (C) a styrene-based monomer in the resin is preferably 1 to 70% by mass, more preferably 3 to 50% by mass, even more preferably 5 to 50% by mass, and even more preferably 15 to 40% by mass. The content of the structural unit derived from (C) a styrene-based monomer is, for example, 8 to 150 parts by mass, preferably 30 to 120 parts by mass, and more preferably 50 to 100 parts by mass per part by mass of the structural unit having a carboxy group and / or a salt thereof (A).

[0045] The total content of the structural units derived from the (C) styrene-based monomer and the (B2) high-Tg (meth)acrylic acid alkyl ester is preferably 5 to 75% by mass, more preferably 15 to 60% by mass, and even more preferably 25 to 50% by mass in the resin. The total content of the structural units derived from the (C) styrene-based monomer and the (B2) high-Tg (meth)acrylic acid alkyl ester is, for example, 8 to 150 parts by mass, preferably 30 to 120 parts by mass, and more preferably 50 to 100 parts by mass, per part by mass of the structural units having a carboxy group and / or a salt thereof (A). By adjusting the content of the structural units derived from the (C) styrene-based monomer or the total content of the structural units derived from the (C) styrene-based monomer and the (B2) high-Tg (meth)acrylic acid alkyl ester within the above ranges, it is possible to further improve the wet rub fastness and color development of the resulting printed textile.

[0046] (D) Structural Unit Derived from Hydroxyl Group-Containing (Meth)acrylic Acid Ester The resin may further contain (D) a structural unit derived from a hydroxyl group-containing (meth)acrylic acid ester. When the resin contains (D) a structural unit derived from a hydroxyl group-containing (meth)acrylic acid ester, adhesion to fabrics (particularly cotton and polyester) can be improved.

[0047] Specific examples of (D) hydroxyl group-containing (meth)acrylic acid esters include (meth)acrylic acid hydroxy C esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate. 1-10 Alkyl esters; halogen-substituted (meth)acrylic acid hydroxy C such as 3-chloro-2-hydroxypropyl (meth)acrylate 1-10 Alkyl esters: modified (meth)acrylic acid hydroxy C such as caprolactone-modified 2-hydroxyethyl (meth)acrylate and 2-(meth)acryloyloxyethyl 2-hydroxyethyl phthalate 1-10Alkyl esters; di- or poly-C such as diethylene glycol (meth)acrylate and polyethylene glycol (meth)acrylate 2-4 alkylene glycol mono(meth)acrylate; and the like. Among them, hydroxy (meth)acrylate C 1-10 Alkyl esters are preferred, and (meth)acrylic acid hydroxy C 1-4 Alkyl esters are more preferred.

[0048] The structural unit (D) derived from a hydroxyl group-containing (meth)acrylic acid ester may be contained in the resin either alone or in combination of two or more.

[0049] The content of the structural units derived from (D) hydroxyl group-containing (meth)acrylic acid ester in the resin is, for example, 0 to 10% by mass, preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, and even more preferably 0.5 to 3% by mass. The content of the structural units derived from (D) hydroxyl group-containing (meth)acrylic acid ester is, for example, 0 to 10 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.3 to 8 parts by mass, and even more preferably 0.5 to 5 parts by mass, per part by mass of the structural units having (A) a carboxy group and / or a salt thereof.

[0050] (E) Structural unit derived from internal crosslinking monomer The resin constituting the resin emulsion particles may further contain (E) a structural unit derived from an internal crosslinking monomer. When the resin contains (E) a structural unit derived from an internal crosslinking monomer, the wet rub fastness of the obtained textile print is further improved.

[0051] (E) internal cross-linking monomer refers to a monomer having one polymerizable unsaturated group and one or more internal cross-linking functional groups in the molecule.The internal cross-linking functional group refers to a functional group that has the function of linking (cross-linking) between the side chains of the resin constituting the resin emulsion particles without the intervention of a cross-linking agent, and examples thereof include a polymerizable unsaturated group, an epoxy group, and a hydrolyzable silyl group.In addition, the hydrolyzable silyl group refers to a silyl group to which a hydrolyzable group (for example, an alkoxy group, a halogen atom, etc.) is bonded.

[0052] Examples of the internally crosslinkable monomer (E) include a monomer having two or more polymerizable unsaturated groups, a silane coupling agent having a hydrolyzable silyl group and a polymerizable unsaturated group, and an epoxy group-containing crosslinkable monomer having an epoxy group and a polymerizable unsaturated group.

[0053] Specific examples of the monomer having two or more polymerizable unsaturated groups include: divinylbenzene; di(meth)acrylates of polyhydric alcohols (preferably dihydric alcohols) 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, and propylene oxide-modified neopentyl glycol di(meth)acrylate; alkyl di(meth)acrylates having 2 to 4 carbon atoms and an added mole number of alkylene oxide groups of 2 to 50, such as polyethylene glycol di(meth)acrylate having 2 to 50 added moles of ethylene oxide and polypropylene glycol di(meth)acrylate having 2 to 50 added moles of propylene oxide; Tri(meth)acrylates of polyhydric alcohols (preferably trihydric alcohols) having 1 to 10 carbon atoms, such as ethoxylated glycerin tri(meth)acrylate, propylene oxide-modified glycerol tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylolpropane triethoxytri(meth)acrylate; tetra(meth)acrylates of polyhydric alcohols (preferably tetrahydric alcohols) having 1 to 10 carbon atoms, such as pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate; hexa(meth)acrylates of polyhydric alcohols (preferably hexahydric alcohols) having 1 to 10 carbon atoms, such as dipentaerythritol hexa(meth)acrylate; di(meth)acrylates having a bisphenol skeleton, such as bisphenol A di(meth)acrylate; 2-(2'-vinyloxyethoxyethyl)(meth)acrylate; and the like.

[0054] Specific examples of the silane coupling agent include (meth)acryloyl group-containing silane coupling agents such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, and 3-(meth)acryloxyethoxypropyltrimethoxysilane; vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; and styryl group-containing silane coupling agents such as p-styryltrimethoxysilane and 2-styrylethyltrimethoxysilane.

[0055] Specific examples of the epoxy group-containing crosslinkable monomer include epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, and 2-glycidyloxyethyl (meth)acrylate; and epoxy group-containing vinyl monomers such as allyl glycidyl ether.

[0056] As the internal crosslinking monomer (E), a monomer having two or more polymerizable unsaturated groups and a silane coupling agent are preferred, divinylbenzene and a (meth)acryloyl group-containing silane coupling agent are more preferred, and divinylbenzene and (meth)acryloxy C are more preferred. 2-4 Alkyldi-C 1-4 Alkoxysilane, (meth)acryloxy C 2-4 Alkyltri C 1-4 Alkoxysilanes are more preferred.

[0057] The structural unit derived from the internal crosslinking monomer (E) may be contained in the resin either alone or in combination of two or more.

[0058] The content of the structural unit derived from the internal crosslinking monomer (E) in the resin is, for example, 0 to 15% by mass, and from the viewpoint of further improving wet rub fastness, it is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass. The content of the structural unit derived from the internal crosslinking monomer (E) is, for example, 0 to 30 parts by mass per part by mass of the structural unit having a carboxy group and / or a salt thereof (A), and from the viewpoint of further improving wet rub fastness, it is preferably 0.5 to 30 parts by mass, and more preferably 1 to 10 parts by mass.

[0059] The total content of the structural units (A) to (E) in the resin is, for example, 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, and may be 100% by mass or 99% by mass or less.

[0060] Among the structural units (A) to (E), the resin preferably contains (A) a structural unit having a carboxy group and / or a salt thereof; and (D) a structural unit derived from a hydroxyl group-containing (meth)acrylic ester, more preferably (A) a structural unit having a carboxy group and / or a salt thereof; (B1) a structural unit derived from a low Tg (meth)acrylic acid alkyl ester; (B2) a structural unit derived from a high Tg (meth)acrylic acid alkyl ester and / or (C) a structural unit derived from a styrene-based monomer; and (D) a structural unit derived from a hydroxyl group-containing (meth)acrylic ester, and even more preferably (A) a structural unit having a carboxy group and / or a salt thereof; (B1) a structural unit derived from a low Tg (meth)acrylic acid alkyl ester; (C) a structural unit derived from a styrene-based monomer; and (D) a structural unit derived from a hydroxyl group-containing (meth)acrylic ester. In the preferred embodiment, the resin preferably further contains (E) a structural unit derived from an internally crosslinkable monomer.

[0061] (F) Structural Unit Derived from Other Polymerizable Monomer The resin constituting the resin emulsion particles may further have a structural unit derived from another polymerizable monomer other than (A1) to (A2) and (B) to (E). The (F) other polymerizable monomer may be a monomer other than the above-mentioned monomers (A1) to (A2) and (B) to (E) and the reactive emulsifiers described below, and may be any monomer having one polymerizable unsaturated group in the molecule.

[0062] Specific examples of (F) other polymerizable monomers include: fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, and octafluoropentyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and naphthyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate, phenylethyl (meth)acrylate, methylbenzyl (meth)acrylate, and naphthylmethyl (meth)acrylate; alkoxyalkyl group-containing (meth)acrylates such as methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, and trimethylolpropane tripropoxy (meth)acrylate; Carbonyl group-containing (meth)acrylates such as (meth)acryloxyalkylpropenal, acetonyl (meth)acrylate, diacetone (meth)acrylate, 2-hydroxypropyl (meth)acrylate acetylacetate, butanediol-1,4-acrylate acetylacetate, and 2-(acetoacetoxy)ethyl (meth)acrylate; amino group-containing (meth)acrylic monomers such as N,N-dimethylaminomethyl (meth)acrylate and N,N-dimethylaminoethyl (meth)acrylate; vinyl lactam monomers such as N-methylvinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinyl-2-pyrrolidone, and N-(meth)acryloylpyrrolidone; maleimide monomers such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; Piperidyl (meth)acrylic monomers such as 2,2,6,6-tetramethyl-4-piperidyl (meth)acrylate and 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate; (meth)acrylic monomers containing an aziridinyl group such as (meth)acryloylaziridine and 2-aziridinylethyl (meth)acrylate;addition-polymerizable oxazolines such as 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; acrylonitrile; (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-n-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, methylenebis(meth)acrylamide, N-butoxymethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropylacrylamide, and diacetone acrylamide; vinyl monomers such as vinyl acetate, vinyl chloride, and vinyl benzoate; Olefin monomers such as ethylene and propylene;

[0063] The structural unit (F) derived from another polymerizable monomer may be contained in the resin either alone or in combination of two or more.

[0064] The content of the structural unit derived from the other polymerizable monomer (F) in the resin is, for example, 0 to 30% by mass, preferably 10% by mass or less, more preferably 5% by mass or less, and may be 1% by mass or less.

[0065] The glass transition temperature (Tg (°C)) of the resin constituting the resin emulsion particles is not particularly limited, but is, for example, −50 to 10°C, preferably −40 to 0°C, and more preferably −30 to −5°C. By setting the Tg of the resin to a predetermined value or less, the obtained printed textile is likely to have excellent texture, and by setting the Tg of the resin to a predetermined value or more, stickiness of the surface of the obtained printed textile treated with the pretreatment liquid can be suppressed.

[0066] The glass transition temperature may be a value obtained by measurement such as differential scanning calorimetry (DSC), differential thermal analysis (DTA), or thermomechanical analysis (TMA). However, it is preferable to use a value obtained by differential scanning calorimetry (DSC). Unless otherwise specified, the glass transition temperature in this specification refers to a value obtained by differential scanning calorimetry (DSC).

[0067] However, if the glass transition temperature can be calculated using the Fox equation based on the composition of the monomer components that make up the resin emulsion particles, this can be used instead.

[0068] An example of a differential scanning calorimetry (DSC) measuring device is the "DSC 3500" manufactured by NETZSCH. Furthermore, when measuring differential scanning calorimetry, there are no particular limitations on the method of plotting a differential scanning calorimetry (DSC) curve, the method of obtaining a first derivative curve from a differential scanning calorimetry (DSC) curve, the method of performing smoothing processing, the method of determining the target peak temperature, etc. For example, when using the above-mentioned measuring device, a plot can be created from data obtained using the measuring device. In this case, analytical software capable of performing mathematical processing can be used. Examples of such analytical software include analytical software (Proteus Analysis). Measurement conditions are preferably a temperature rise rate of 10°C / min and a temperature fall rate of 10°C / min. Furthermore, in the above measurement, the onset temperature, intermediate temperature, inflection point temperature, and end temperature of the glass transition are observed, and the intermediate temperature can be taken as the glass transition temperature (Tg) of the resin emulsion particles.

[0069] The resin emulsion particles contain a nonionic emulsifier. The form in which the nonionic emulsifier is contained is not particularly limited, and it may be contained in a form that interacts with the surface of the resin particles. Furthermore, when the nonionic emulsifier is a reactive emulsifier described below, it may be contained as a polymerized unit in the resin that constitutes the resin emulsion particles through a polymerization reaction with the above-mentioned monomer component. The resin emulsion particles can contain the nonionic emulsifier by using at least a nonionic emulsifier as an emulsifier used during emulsion polymerization to produce the resin emulsion particles. The resin emulsion particles contain a nonionic emulsifier, i.e., by using a nonionic emulsifier in the production of the resin emulsion particles, the storage stability of the resulting pretreatment liquid can be improved. In this specification, the term "monomer component" refers to a compound having at least one polymerizable unsaturated group in its molecule, other than the reactive emulsifiers described below. Specific examples include the monomers (A1) to (A3) and (B) to (F) described above.

[0070] The nonionic emulsifier includes conventionally known nonionic emulsifiers, and more specifically, refers to a compound having a nonionic hydrophilic group and a hydrophobic group. Examples of the hydrophilic group include groups known as hydrophilic groups possessed by nonionic emulsifiers (surfactants), such as polyether groups and ester groups. Examples of the hydrophobic group include groups known as hydrophobic groups possessed by nonionic emulsifiers (surfactants), and preferred examples include alkyl groups (particularly alkyl groups having about 8 to 40 carbon atoms), aryl group-containing hydrocarbon groups (particularly hydrocarbon groups having about 12 to 40 carbon atoms and a phenyl group), and polycyclic phenyl groups.

[0071] In particular, from the viewpoint of further improving storage stability and wet rub fastness, the nonionic emulsifier is preferably a reactive emulsifier. The use of a reactive emulsifier enables a polymerization reaction with the above-mentioned monomer component, and the resin constituting the resin emulsion particles contains structural units derived from the nonionic emulsifier. Examples of the reactive emulsifier include conventionally known nonionic reactive emulsifiers, and more specifically, compounds having a polymerizable unsaturated group, the hydrophilic group, and the hydrophobic group. One molecule of the reactive emulsifier may contain one or more polymerizable unsaturated groups.

[0072] Specific examples of the nonionic emulsifier include nonionic emulsifiers having a polymerizable unsaturated group (hereinafter referred to as nonionic reactive emulsifiers), such as polyoxyethylene styrenated propenyl phenyl ether (e.g., trade names: Aqualon AN-10, Aqualon AN-20, etc., manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), allyloxymethyl alkoxyethyl hydroxypolyoxyethylene (e.g., trade name: Adeka Reasop ER-20, etc., manufactured by ADEKA Corporation), polyoxyethylene alkylpropenyl phenyl ether (e.g., trade name: Aqualon RN-10, Aqualon RN-20, etc., manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene (e.g., trade name: Adeka Reasop NE-10, etc., manufactured by ADEKA Corporation), and polyoxyalkylene alkenyl ether (e.g., trade name: Latemul PD-420, etc., manufactured by Kao Corporation); Examples of the emulsifier include nonionic emulsifiers having no polymerizable unsaturated group (hereinafter referred to as nonionic non-reactive emulsifiers), such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, condensates of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, and condensates of ethylene oxide and aliphatic amines.

[0073] The resin emulsion particles may contain one type of nonionic emulsifier alone or two or more types of nonionic emulsifiers.

[0074] The content of the nonionic emulsifier in the pre-treatment liquid is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 5 to 15 parts by mass, relative to 100 parts by mass of the total of structural units derived from the monomer components constituting the resin.

[0075] The pretreatment liquid of the present invention may contain one type of resin emulsion particle alone or two or more types of resin emulsion particles.

[0076] The content of the resin emulsion particles is, for example, 2 to 80% by mass, preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 45% by mass, of the solids (non-volatile content) of the pretreatment liquid. By setting the content of the resin emulsion particles to a predetermined value or more, the color development and wet rub fastness of the printed textile can be further improved, while by setting the content of the resin emulsion particles to a predetermined value or less, the storage stability of the pretreatment liquid and the texture of the printed textile can be further improved. In this specification, the solids (non-volatile content) refers to the components excluding the solvent.

[0077] (Method for producing resin emulsion particles) The resin emulsion particles are preferably produced by emulsion polymerizing the above-mentioned monomer components in an aqueous medium in the presence of a nonionic emulsifier and a polymerization initiator. The types, combinations, and blending ratios of the preferred monomer components used in emulsion polymerization are the same as those described above for the preferred monomer components for forming the resin constituting the resin emulsion particles. The specific means and conditions for carrying out emulsion polymerization can be appropriately selected and adopted from the means and techniques used in conventionally known emulsion polymerization methods. A preferred production method will be described in detail below.

[0078] The nonionic emulsifier used in the emulsion polymerization may be any of those described above as the nonionic emulsifier contained in the resin emulsion particles, and preferred embodiments are also the same. The nonionic emulsifiers may be used alone or in combination of two or more.

[0079] The content of the nonionic reactive emulsifier in 100% by mass of the nonionic emulsifier used in the emulsion polymerization is, for example, 30% by mass or more, preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass.

[0080] The amount of the nonionic emulsifier used is, for example, 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 5 to 15 parts by mass, per 100 parts by mass of the monomer component. If necessary, a protective colloid can be used alone or together with the emulsifier.

[0081] It is preferable to refrain from using an anionic emulsifier when carrying out the emulsion polymerization, i.e., the resin emulsion particles are substantially free of anionic emulsifier. The amount of anionic emulsifier used is preferably 1 part by mass or less per 100 parts by mass of the monomer components, and is preferably 0 part by mass, i.e., no anionic emulsifier is used. By adjusting the amount of anionic emulsifier used within the above range, the storage stability of the resulting pretreatment liquid can be further improved.

[0082] The polymerization initiator used in carrying out the emulsion polymerization is not limited, but examples thereof include azo initiators such as azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-diaminopropane) hydrochloride, 4,4-azobis(4-cyanovaleric acid), and 2,2-azobis(2-methylpropionamidine) dihydrochloride; persulfates such as ammonium persulfate and potassium persulfate; and peroxide initiators such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide. When a peroxide-based polymerization initiator is used as a polymerization initiator, if it is necessary to increase the polymerization rate or lower the reaction temperature, a reducing agent such as a soluble sulfite or ascorbic acid, or a metal compound that generates heavy metal ions in water such as ferrous sulfate, can be combined with the peroxide-based polymerization initiator to form a redox-based initiator.

[0083] These polymerization initiators may be used alone or in combination of two or more.

[0084] The polymerization initiator used in the emulsion polymerization is preferably an azo initiator or a persulfate. In particular, from the viewpoint of further improving the storage stability of the resulting pretreatment liquid, the azo initiator is preferred as the polymerization initiator. That is, the resin constituting the resin particles preferably contains an azo initiator or a decomposition product thereof.

[0085] The amount of the polymerization initiator used in the emulsion polymerization is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of the monomer components.

[0086] The reaction temperature during the emulsion polymerization can be appropriately set taking into consideration the blending ratio of the monomer components, the type of polymerization initiator, and the like. The reaction temperature is, for example, 0 to 100°C, preferably 50 to 95°C, and more preferably 60 to 90°C, and the reaction time is, for example, 0.5 to 30 hours, preferably 1 to 20 hours, and more preferably 3 to 10 hours. The reaction pressure is also not particularly limited and may be normal pressure (atmospheric pressure), reduced pressure, or increased pressure. The polymerization reaction is desirably carried out in an atmosphere of an inert gas such as nitrogen gas.

[0087] The aqueous medium used in the emulsion polymerization may be water or a mixed solvent of water and a water-soluble organic solvent. The water content in the aqueous medium is preferably 10 to 100% by mass, more preferably 25% by mass or more, even more preferably 60% by mass or more, and particularly preferably 90% by mass or more. The remainder is preferably the water-soluble organic solvent.

[0088] Examples of the water-soluble organic solvent include lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and tert-butyl alcohol (preferably C 1-4alcohols); glycols such as propylene glycol, 1,3 propanediol, dipropylene glycol, tripropylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol (preferably mono-, di-, or poly-C 2-4 alkylene glycol); monoalkylene glycol monoalkyl ethers such as monoethylene glycol monomethyl ether, monoethylene glycol monoethyl ether, monoethylene glycol monopropyl ether, monoethylene glycol monobutyl ether, monopropylene glycol monomethyl ether, monopropylene glycol monoethyl ether, monopropylene glycol monopropyl ether, and monopropylene glycol monobutyl ether (preferably, mono-C 2-4 Alkylene glycol mono C 1-4 alkyl ethers); dialkylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether (preferably diC 2-4 Alkylene glycol mono C 1-4 alkyl ethers); monoalkyl ethers of polyethylene glycol such as monomethyl ether of polyethylene glycol, monoethyl ether of polyethylene glycol, monopropyl ether of polyethylene glycol, and monobutyl ether of polyethylene glycol (preferably mono-C polyethylene glycol having an EO addition mole number of 2 to 10); 1-4 alkyl ethers); monoalkyl ethers of polypropylene glycol such as monomethyl ether of polypropylene glycol, monoethyl ether of polypropylene glycol, monopropyl ether of polypropylene glycol, and monobutyl ether of polypropylene glycol (preferably mono-C polypropylene glycol having a PO addition mole number of 2 to 10); 1-4Examples of the water-soluble organic solvent include: alkyl ethers; polyhydric alcohols such as glycerin; heterocyclic compounds such as 2-pyrrolidone and N-methyl-2-pyrrolidone; and ketones such as acetone and methyl ethyl ketone. These water-soluble organic solvents may be used alone or in combination of two or more.

[0089] The amount of the aqueous medium used in carrying out the emulsion polymerization is not limited, but is preferably 50 to 500 parts by mass, more preferably 80 to 400 parts by mass, and even more preferably 100 to 300 parts by mass, per 100 parts by mass of the monomer components.

[0090] Specific examples of the emulsion polymerization include monomer dropping polymerization, pre-emulsion dropping polymerization, seed polymerization, and multi-stage polymerization.

[0091] In the emulsion polymerization, if necessary, additives such as a chain transfer agent, for example, a compound having a thiol group such as tert-dodecyl mercaptan, a pH buffer, a chelating agent, etc. may be added in appropriate amounts to the reaction system.

[0092] In such an emulsion polymerization method, an emulsion is obtained in which the resulting resin particles are dispersed in an aqueous medium as emulsion particles. The resin emulsion particles of the present invention are not particularly limited in their form. The resin emulsion particles of the present invention include not only particles dispersed in the reaction liquid after the above-mentioned emulsion polymerization, but also particles contained in a dispersion system obtained by removing a portion of the aqueous medium from the reaction liquid, or particles contained in a dispersion system obtained by solvent-substitution of a portion or all of the aqueous medium of the reaction liquid with another dispersion medium. The resin emulsion particles of the present invention also include particles (including powdery forms) obtained by removing all of the aqueous medium from the reaction liquid. The resin emulsion particles of the present invention also include resin emulsion particles obtained by emulsion polymerization that have been subjected to the above-mentioned modifications, such as neutralization. Examples of the neutralization treatment include adding an aqueous solution containing a basic substance (e.g., an alkali metal hydroxide such as sodium hydroxide, an alkaline earth metal hydroxide such as barium hydroxide, an amine such as cyclohexylamine, or ammonia) to the emulsion obtained by emulsion polymerization. The neutralization treatment may be used to modify some or all of the carboxy groups contained in the resin emulsion particles into salts of the carboxy groups, such as alkali metal salts, alkaline earth metal salts, and ammonium salts, thereby introducing structural units having a salt of a carboxy group into the resin.

[0093] [Oxazoline Group-Containing Compound] The pretreatment liquid of the present invention contains an oxazoline group-containing compound. The inclusion of the oxazoline group-containing compound improves storage stability and forms crosslinked structures between the resin emulsion particles, thereby improving the wet rub fastness and color development of the resulting printed textile.

[0094] The oxazoline group-containing compound means a compound having two or more oxazoline groups in the molecule. Examples of the oxazoline group-containing compound include 2,2'-bis(2-oxazoline), 2,2'-methylene-bis(2-oxazoline), 2,2'-ethylene-bis(2-oxazoline), 2,2'-trimethylene-bis(2-oxazoline), 2,2'-tetramethylene-bis(2-oxazoline), 2,2'-hexamethylene-bis(2-oxazoline), 2,2'-octamethylene-bis(2-oxazoline), 2,2'-ethylene-bis( 4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(4,4'-dimethyl-2-oxazoline), bis(2-oxazolinylcyclohexane) sulfide, bis(2-oxazolinylnorbornane) sulfide, oxazoline group-containing polymers, and the like are not limited to these examples.

[0095] The pretreatment liquid of the present invention may contain one or more of the oxazoline group-containing compounds.

[0096] Among the oxazoline group-containing compounds, a water-soluble oxazoline group-containing compound is preferred from the viewpoint of excellent crosslinking performance. The water-soluble oxazoline group-containing compound is preferably an oxazoline group-containing compound that dissolves 1 g or more in 100 mL of water at 25° C.

[0097] The oxazoline group-containing compound is preferably an oxazoline group-containing polymer having two or more oxazoline groups in the molecule. The oxazoline group-containing polymer can be produced by a conventionally known production method. For example, a method of polymerizing one or more addition-polymerizable oxazolines, or a method of polymerizing a monomer component containing an addition-polymerizable oxazoline and a monomer copolymerizable with the addition-polymerizable oxazoline, can be mentioned.

[0098] Examples of the addition-polymerizable oxazoline include compounds having a polymerizable unsaturated group and an oxazoline group in the molecule, such as 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. Monomers copolymerizable with the addition-polymerizable oxazoline are preferably monomers copolymerizable with the addition-polymerizable oxazoline but lacking a functional group reactive with the oxazoline group. Examples of the monomer components include oxazoline groups and / or monomers lacking a functional group reactive with the oxazoline group. Specific examples include (meth)acrylic acid alkyl esters, styrene-based monomers, (meth)acrylamide-based monomers, vinyl-based monomers, and olefin-based monomers.

[0099] Among the oxazoline group-containing polymers, water-soluble oxazoline group-containing polymers are preferred from the viewpoint of excellent crosslinking performance. Examples of the water-soluble oxazoline group-containing polymer include polymers having a (meth)acrylic polymer or a (meth)acrylic-styrene polymer as a main chain and containing oxazoline groups in the side chains.

[0100] Commercially available oxazoline group-containing polymers can also be used. Examples include water-soluble polymers such as EPOCROS WS-500 and EPOCROS WS-700, and emulsion polymers such as EPOCROS K-2010, EPOCROS K-2020, and EPOCROS K-2030, all manufactured by Nippon Shokubai Co., Ltd. Of these, the water-soluble polymers EPOCROS WS-500 and EPOCROS WS-700 are preferred.

[0101] The content of the oxazoline group-containing compound (preferably an oxazoline group-containing polymer) is preferably 0.1 to 50 parts by mass, more preferably 0.3 to 40 parts by mass, and even more preferably 0.5 to 30 parts by mass, relative to 100 parts by mass of the resin emulsion particles. By adjusting the content of the oxazoline group-containing compound within the above range, the storage stability of the pretreatment liquid can be further improved. Furthermore, by setting the content of the oxazoline group-containing compound to a predetermined value or more, the wet rub fastness and color development of the printed textile can be further improved.

[0102] [Aqueous Medium] The pretreatment liquid of the present invention contains an aqueous medium. Examples of the aqueous medium include water and a mixed solvent of water and a water-soluble organic solvent. In particular, by using a mixed solvent of water and a water-soluble organic solvent as the aqueous medium, the wet rub fastness and color development of the obtained printed textile tend to be further improved. The content of the water-soluble organic solvent in the aqueous medium is, for example, 0 to 50% by mass, preferably 3 to 40% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass.

[0103] Examples of the water-soluble organic solvent include the same solvents as the water-soluble organic solvents in the aqueous medium used in emulsion polymerization of the resin emulsion particles. The water-soluble organic solvents may be contained alone or in combination of two or more.

[0104] As the water-soluble organic solvent, it is preferable to use a water-soluble organic solvent having a boiling point of 150° C. or higher, more preferably a water-soluble organic solvent having a boiling point of 150 to 300° C., and even more preferably a water-soluble organic solvent having a boiling point of 160 to 260° C. By using such a water-soluble organic solvent, it is likely that a printed product having improved wet rub fastness can be obtained. In particular, from the viewpoint of further improving wet rub fastness, glycol is preferable, and mono- or di-C 2-4 Alkylene glycol is more preferred, and diethylene glycol and propylene glycol are even more preferred.

[0105] The content of the aqueous medium in the pre-treatment liquid of the present invention may be set depending on the desired viscosity of the pre-treatment liquid. From the viewpoint of handleability, the content of the aqueous medium in the pre-treatment liquid of the present invention is, for example, 40 to 98 mass %, preferably 70 to 95 mass %, and more preferably 85 to 95 mass %.

[0106] [Other Additives] The pretreatment liquid of the present invention may further contain additives within the scope of not impairing the object of the present invention, such as surfactants, dispersants, leveling agents, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, antifoaming agents, antioxidants, crosslinking accelerators, pH adjusters, and preservatives, in appropriate amounts.

[0107] When the additive is added, its content is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less in the pretreatment liquid of the present invention. In order to exert the effect of addition, its content is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more.

[0108] The pretreatment liquid of the present invention may further contain a binder resin other than the resin constituting the resin emulsion particles, such as a vinyl resin, a (meth)acrylic resin, an olefin resin, a urethane resin, a fluorine-containing resin, a silicone resin, an epoxy resin, a phenoxy resin, a phenolic resin, or a xylene resin, as long as the object of the present invention is not impaired. The resin emulsion particles are also included in the binder resin in the pretreatment liquid. The content of the resin emulsion particles in 100% by mass of the binder resin contained in the pretreatment liquid of the present invention is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, and may even be 100% by mass.

[0109] The viscosity of the pretreatment liquid of the present invention may be adjusted appropriately depending on the method of applying the pretreatment liquid, but is preferably in the range of 0.1 to 20 mPa·s, and more preferably in the range of 0.5 to 10 mPa·s.

[0110] [Method for Producing Pretreatment Liquid] The method for producing the pretreatment liquid of the present invention is not particularly limited. For example, the pretreatment liquid can be produced by mixing a water-soluble polyvalent metal salt, a resin emulsion particle, an oxazoline group-containing compound, an aqueous medium, and other additives used as needed. Specifically, the pretreatment liquid is preferably produced by mixing a water-soluble polyvalent metal salt, an emulsion containing resin emulsion particles, an oxazoline group-containing compound, an aqueous medium, and other additives used as needed.

[0111] The emulsion containing the resin emulsion particles is an emulsion in which resin particles are dispersed in an aqueous medium, and can be produced by a conventionally known emulsion polymerization method as described above. Note that the emulsion is not limited to the reaction solution after emulsion polymerization, as long as the resin emulsion particles are dispersed in a dispersion medium. For example, the "emulsion" also includes those obtained by diluting the reaction solution after emulsion polymerization with water or an organic solvent, those obtained by removing part of the aqueous medium in the reaction solution to increase the concentration, those obtained by replacing part or all of the aqueous medium in the reaction solution with another solvent, those obtained by adding an additive to the reaction solution, and those obtained by adding a neutralizer such as a basic substance-containing aqueous solution to modify the resin emulsion particles.

[0112] From the viewpoint of handleability, the content of the resin emulsion particles in the emulsion is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, and even more preferably 25 to 50% by mass. The content of the resin emulsion particles in the emulsion can be determined as the non-volatile content (solid content) of the emulsion, that is, it is preferable to adjust the solid content of the emulsion to be within the above range.

[0113] In addition, when mixing, the water-soluble polyvalent metal salt, the oxazoline group-containing compound, and other additives may be used as they are, or may be added as a solution dispersed or dissolved in an aqueous medium. The method and order of mixing the above components are not particularly limited. After mixing, centrifugation, filtration, etc. may be performed as needed.

[0114] The pretreatment liquid of the present invention can be suitably used as a pretreatment liquid in inkjet textile printing. The present invention also encompasses a method of using the pretreatment liquid as a pretreatment liquid in inkjet textile printing, specifically, a method of treating a fabric with the pretreatment liquid and then performing inkjet textile printing. The pretreatment liquid used in the method is as described above, including preferred embodiments thereof. The method of treating a fabric with the pretreatment liquid in the method is similar to the steps described below in the "(Pretreatment Step)" section, including preferred embodiments thereof. The method of performing inkjet textile printing in the method is similar to the steps described below in the "(Image Forming Step)" section, including preferred embodiments thereof.

[0115] [Printed Material] A printed material printed using the pretreatment liquid of the present invention is composed of a fabric having the solid components of the pretreatment liquid adhered to its surface, and ink adhered to the solid components. A printed material printed using the pretreatment liquid of the present invention has excellent color development and wet rub fastness, and preferably also has excellent texture. The printed material can be produced by various methods, but a preferred method among these methods will be described below.

[0116] The method for producing a printed item includes a pretreatment step of treating a fabric with the pretreatment liquid described above, and an image formation step of performing inkjet printing on the treated surface of the fabric obtained in the pretreatment step (i.e., forming an image by applying an inkjet printing ink).

[0117] (Pretreatment step) The fabric used in the pretreatment step may be any textile product such as cloth or fabric made from natural and / or synthetic fibers, including woven fabric, nonwoven fabric, knitted fabric, etc. The fibers constituting the fabric are not particularly limited, and include, for example, natural fibers, chemical fibers, or mixtures thereof.

[0118] Preferred examples of natural fibers include silk, cotton, and wool. Preferred 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. Among these, fabrics containing at least one of cotton, polyester fibers, and polypropylene fibers are preferred.

[0119] The pretreatment step includes a step of applying the pretreatment liquid to at least one surface of the fabric. The pretreatment liquid may be applied to the entire surface of the fabric to be treated, or may be applied to a portion of the surface. Alternatively, the pretreatment liquid may be applied selectively only to an area onto which the inkjet printing ink described below is to be ejected. The method for applying the pretreatment liquid to the fabric is not particularly limited, and examples thereof include a method of immersing the fabric in the pretreatment liquid, a method of applying the pretreatment liquid to the fabric using a roll coater or the like, a method of spraying the pretreatment liquid onto the fabric using a spray device or the like, a method of ejecting the pretreatment liquid onto the fabric by an inkjet method, and a method of applying the pretreatment liquid to the fabric by a pad method.

[0120] The amount of the pretreatment liquid applied is, for example, 0.005 to 0.060 g / cm 3 , preferably 0.010 to 0.050 g / cm 3 is.

[0121] In the pretreatment step, it is preferable to apply the pretreatment liquid to the fabric and then dry the fabric. This improves the fixation of the pretreatment liquid. The drying method is not particularly limited, but examples include hot air drying, heat pressing, atmospheric steaming, and pressurized steaming. The drying temperature is preferably 110 to 200°C, more preferably 130 to 180°C. By setting the drying temperature to a predetermined value or higher, the fixation of the pretreatment liquid can be further improved, and by setting the drying temperature to a predetermined temperature or lower, deterioration of the fabric and resins contained in the pretreatment liquid can be suppressed. The drying time is not particularly limited, but from the viewpoint of productivity, 5 seconds to 5 minutes is preferable.

[0122] By undergoing the above-described pretreatment step, a fabric to which the pretreatment liquid has been applied is obtained, more specifically, a fabric to which the solid content of the pretreatment liquid has adhered to the surface is obtained.

[0123] (Image Forming Step) The image forming step includes a step of depositing an ink for inkjet textile printing (hereinafter, sometimes simply referred to as ink) on the treated surface of the fabric obtained in the pretreatment step (i.e., the surface to which the solid content of the pretreatment liquid has been deposited). As the ink, any ink used in conventional inkjet textile printing can be used. The ink may be an aqueous ink (an ink in which the main component of the solvent contained in the ink is water) or a solvent-based ink (an ink in which the main component of the solvent contained in the ink is an organic solvent), but an aqueous ink is preferred from the viewpoint of reducing the environmental load.

[0124] The aqueous ink contains an aqueous medium and a colorant. Examples of the aqueous medium include the same solvents as those contained in the pretreatment liquid. The colorant may be a dye or a pigment, but is preferably a pigment. Examples of the pigment include organic pigments and inorganic pigments, which may be used alone or in combination of two or more types. If necessary, they may also be used in combination with an extender pigment.

[0125] The aqueous ink may further contain a binder resin. The binder resin preferably exists as emulsion particles in the aqueous medium. Examples of the binder resin 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-chlorinated ethylene-styrene copolymers, polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-vinyl acetate-(meth)acrylic acid ester copolymers, (meth)acrylic acid ester (co)polymers, (meth)acrylic acid ester-(meth)acrylic acid copolymers, (meth)acrylic acid ester-styrene copolymers, (meth)acrylic acid ester-(meth)acrylic acid-styrene copolymers, ethylene-vinyl acetate-(meth)acrylic acid ester copolymers, (meth)acrylic acid ester-urethane copolymers, acrylonitrile-(meth)acrylic acid ester-styrene copolymers, and polyurethanes. Among these, acrylic resins and urethane resins (polyurethanes) containing as their main components structural units derived from (meth)acrylic monomers such as (meth)acrylic acid esters and (meth)acrylic acid are preferred. These may be used alone or in combination of two or more.

[0126] The aqueous ink may contain other components in addition to the above-mentioned components (aqueous medium, colorant, and binder resin), such as surfactants, dispersants, leveling agents, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, antifoaming agents, antioxidants, crosslinking agents, crosslinking accelerators, pH adjusters, and preservatives in appropriate amounts.

[0127] In the image forming step, the ink is preferably applied to the treated surface of the fabric using an inkjet printer. The inkjet printer is not particularly limited, and any conventionally known inkjet printer can be used. The inkjet printer may be, for example, a piezoelectric, thermal, or charge change control (continuous ejection) type, with a piezoelectric inkjet printer being particularly preferred. When using a piezoelectric inkjet printer, the ink ejection conditions are not particularly limited and may be appropriately selected depending on the ink properties, the type of fabric, the type of image to be printed, and other factors. The ink viscosity is preferably in the range of 2 to 20 mPa·s, more preferably 2 to 10 mPa·s. The surface tension of the ink is preferably in the range of 25 to 45 mN / m.

[0128] In the image forming process, the ink ejected from the nozzle openings of the inkjet printer head adheres to the treated surface of the fabric to form an image.

[0129] It is preferable to further heat the fabric on which the image has been formed in the image forming step at a temperature higher than room temperature, which can promote the removal of volatile components, such as ink-derived solvents, contained in the image formed on the fabric, and can promote the fixation of the image.

[0130] The heating may be performed simultaneously with the image forming process or after the image forming process. Alternatively, both may be combined. For example, a method of performing heating simultaneously with the image forming process includes a method of performing the image forming process while heating the fabric. When heating is performed after the image forming process, preferred examples include a heating method using a heating drying oven such as a hot air dryer, a heating method using a heat press, a heating method using an infrared lamp, and a method using steam such as atmospheric steam or high-pressure steam. Among these, the heating method is preferably performed after the image forming process, since simultaneous heating may cause disturbances in the air flow.

[0131] The heating temperature is preferably 90 to 200°C, more preferably 120 to 180°C. By adjusting the heating temperature within the above range, a printed product with excellent wet rub fastness can be obtained in a short time. However, the heating temperature is not limited to the above range and may be, for example, a temperature near room temperature, such as 15 to 25°C. Even at such a temperature, a printed product with sufficient wet rub fastness can be obtained by leaving it to stand (heating) for a long period of time. However, from the viewpoint of shortening the heating time, a temperature of 30°C or higher is preferred, more preferably 50°C or higher, and even more preferably 90°C or higher.

[0132] After the above heating, the printed item obtained may be washed with water and dried.

[0133] The above-described production method makes it possible to obtain a printed textile that is composed of a fabric having the solid content of the pretreatment liquid adhered to its surface and an ink adhered to this solid content, and that has excellent color development and wet rub fastness.

[0134] This application claims the benefit of priority based on Japanese Patent Application No. 2023-123161, filed on July 28, 2023. The entire contents of the specification of Japanese Patent Application No. 2023-123161, filed on July 28, 2023, are incorporated herein by reference.

[0135] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass." The measurement and evaluation methods are as follows:

[0136] <Average particle size of resin emulsion particles> The average particle size of resin emulsion particles is a value obtained by the cumulant method when the resin emulsion is measured using a particle size distribution measuring instrument (manufactured by Otsuka Electronics Co., Ltd., product number: FPAR-1000) by dynamic light scattering.

[0137] <Glass Transition Temperature (Tg) of Resin Emulsion Particles> The glass transition temperature (Tg) of the emulsion particles was measured by differential scanning calorimetry (DSC) under the following measurement conditions. Measuring instrument: DSC 3500 (trade name, manufactured by NETZSCH) Sample container: sealed aluminum container Sample weight: 10 mg ± 2 mg Measurement method: Two cycles of temperature increase from -50°C to 150°C were performed in a N2 atmosphere. The temperature increase / decrease rate was 10°C / min, and the holding times at -50°C and 150°C were 5 minutes. Using the analysis software proteus Analysis, the glass transition temperature was analyzed from the DSC curve chart during the second temperature increase cycle, and the value of the midpoint glass transition temperature was used.

[0138] <Viscosity of Pretreatment Liquid> The viscosity of each pretreatment liquid obtained in each example and comparative example was measured using an E-type viscometer TPE-100 (manufactured by Toki Sangyo Co., Ltd.) with a rotor R24, 0.8 degrees, and 25°C.

[0139] <Evaluation of physical properties> (1) Evaluation of storage stability of pretreatment liquid Each pretreatment liquid obtained was sealed in an airtight container and stored in a thermostatic chamber at 50°C for 30 days, and evaluated according to the following evaluation criteria: ◎: No aggregates were observed even after storage, and the viscosity change rate before and after storage was 10% or less. ○: No aggregates were observed even after storage, and the viscosity change rate before and after storage was 11 to 20%. △: A small amount of aggregates was observed after storage, but at a level that is not problematic in practical use. ×: Gelation occurred during preparation of the pretreatment liquid.

[0140] (2) Evaluation of wet rubbing fastness of printed fabrics The printed fabrics obtained in each example and comparative example were subjected to a wet rubbing test in accordance with the method specified in JIS L0849 using a type II testing machine with a cotton No. 3-1 attached white cloth, with a load of 200 g and 100 strokes back and forth, and evaluated using a discoloration gray scale. In Comparative Example 6, gelation occurred during the preparation of the pretreatment liquid, making it impossible to evaluate the wet rubbing fastness of the printed fabric. ◎: Wet rubbing test: Staining grade 4-5 or higher ○: Wet rubbing test: Staining grade 3-4 or grade 4 △: Wet rubbing test: Staining grade 2-3 or grade 3 ×: Wet rubbing test: Staining grade 2 or lower

[0141] (3) Evaluation of color development of printed textiles The printed textiles obtained in each example and each comparative example were evaluated for color development. * The SE-6000 manufactured by Nippon Denshoku Industries Co., Ltd. was used as a measuring instrument, and the color development property was evaluated by measuring the CIE / L * a * b * L in color system * The values ​​were measured. The measurement conditions were an observation light source of C, an observation field of view of 2°, and density Status A. The measurement was carried out three times for each printed item, and the average value was used as the measured value for evaluation. In Comparative Example 6, the pretreatment liquid gelled during preparation, making it impossible to evaluate the color development of the printed item. ◯: L * =91 or more △:L * = 90 or more and less than 91 ×: L * = Less than 90

[0142] (4) Evaluation of the feel of the printed textile The printed textiles obtained in each Example and Comparative Example were evaluated by touch. In Comparative Example 6, the pretreatment liquid gelled during preparation, making it impossible to evaluate the feel of the printed textile. ◯: The printed textile bends easily and is close to the softness of the fabric itself. △: The printed textile bends easily, but feels slightly stiffer than the fabric itself. ×: The printed textile is so stiff that it cannot bend freely.

[0143] <Emulsion Production Examples> [Emulsion Production Example 1] Into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 1,125 parts of deionized water was placed. A pre-emulsion for dropping was prepared in a dropping funnel, consisting of 290 parts of deionized water, 400 parts of a 25% aqueous solution of an emulsifier (manufactured by ADEKA Corporation, trade name: ADEKA REASOAP ER-20), 5 parts of acrylic acid, 565 parts of 2-ethylhexyl acrylate, 70 parts of cyclohexyl methacrylate, 10 parts of hydroxyethyl methacrylate, and 350 parts of styrene. 51 parts of this pre-emulsion, corresponding to 3% of the total amount of the pre-emulsion, was added to the flask, and the temperature was raised to 80°C while slowly blowing in nitrogen gas. 50 parts of a 5% aqueous solution of an azo initiator (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 2,2'-azobis(2-methylpropionamidine) dihydrochloride, trade name: V-50) (hereinafter referred to as 5% V-50 aqueous solution) was added to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping and 30 parts of a 5% V-50 aqueous solution were uniformly added dropwise to the flask over a period of 240 minutes. After completion of the dropwise addition, the contents of the flask were maintained at 80°C for 180 minutes, and the pH was adjusted to 8.5 and the solids content to 35% by adding 25% aqueous ammonia and deionized water, thereby terminating the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire screen to obtain Emulsion 1 containing Resin Emulsion Particles 1. Resin Emulsion Particles 1 had a Tg of -21°C and an average particle size of 210 nm.

[0144] Emulsion Production Example 2 Emulsion 2 containing resin emulsion particles 2 was obtained in the same manner as in Emulsion Production Example 1, except that the amount of acrylic acid in the pre-emulsion for dropping in Emulsion Production Example 1 was changed to 18 parts and the amount of cyclohexyl methacrylate was changed to 57 parts. The Tg of resin emulsion particles 2 was −20° C. and the average particle size was 300 nm.

[0145] [Emulsion Production Example 3] Emulsion 3 containing resin emulsion particles 3 was obtained in the same manner as in Emulsion Production Example 1, except that in the pre-emulsion for dropping in Emulsion Production Example 1, the amount of 2-ethylhexyl acrylate was changed to 235 parts, the amount of cyclohexyl methacrylate was changed to 0 parts, and 400 parts of n-butyl acrylate was newly added. The Tg of Resin Emulsion Particles 3 was −8° C. and the average particle size was 200 nm.

[0146] Emulsion Production Example 4 Emulsion 4 containing resin emulsion particles 4 was obtained in the same manner as in Emulsion Production Example 1, except that a 25% aqueous solution of Aqualon RN-10 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used as the emulsifier instead of the 25% aqueous solution of Adeka Reasoap ER-20 in the pre-emulsion for dropping in Emulsion Production Example 1. Resin emulsion particles 4 had a Tg of −20° C. and an average particle size of 200 nm.

[0147] Emulsion Production Example 5 Emulsion 5 containing resin emulsion particles 5 was obtained in the same manner as in Emulsion Production Example 1, except that the amount of styrene in the pre-emulsion for dropping in Emulsion Production Example 1 was changed to 50 parts and 300 parts of methyl methacrylate was newly added. Resin emulsion particles 5 had a Tg of −22° C. and an average particle size of 210 nm.

[0148] Emulsion Production Example 6 Emulsion 6 containing resin emulsion particles 6 was obtained in the same manner as in Emulsion Production Example 1, except that the amount of cyclohexyl methacrylate in the pre-emulsion for dropping in Emulsion Production Example 1 was changed to 50 parts and 20 parts of divinylbenzene was newly added. The Tg of resin emulsion particles 6 was −15° C. and the average particle size was 230 nm.

[0149] Emulsion Production Example 7 Emulsion 7 containing resin emulsion particles 7 was obtained in the same manner as in Emulsion Production Example 1, except that the amount of cyclohexyl methacrylate in the pre-emulsion for dropping in Emulsion Production Example 1 was changed to 50 parts and 20 parts of KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) was newly added. Resin emulsion particles 7 had a Tg of −14° C. and an average particle size of 220 nm.

[0150] Emulsion Production Example 8 Emulsion 8 containing resin emulsion particles 8 was obtained in the same manner as in Emulsion Production Example 1, except that methacrylic acid was used instead of acrylic acid in the pre-emulsion for dropping in Emulsion Production Example 1. The Tg of resin emulsion particles 8 was −21° C. and the average particle size was 210 nm.

[0151] Emulsion Production Example 9 Emulsion 9 containing resin emulsion particles 9 was obtained in the same manner as in Emulsion Production Example 1, except that a 5% aqueous solution of ammonium persulfate was used instead of the 5% aqueous solution of V-50 added as an initiator in Emulsion Production Example 1. Resin emulsion particles 9 had a Tg of −20° C. and an average particle size of 200 nm.

[0152] Emulsion Production Example 10 Emulsion 10 containing resin emulsion particles 10 was obtained in the same manner as in Emulsion Production Example 1, except that a 25% aqueous solution of Newcol 723 (manufactured by Nippon Nyukazai Co., Ltd.) was used as the emulsifier instead of the 25% aqueous solution of Adeka Reasoap ER-20 in the pre-emulsion for dropping in Emulsion Production Example 1. The Tg of the resin emulsion particles 10 was −20° C. and the average particle size was 200 nm.

[0153] [Emulsion Production Example 11] Emulsion 11 containing resin emulsion particles 11 was obtained in the same manner as in Emulsion Production Example 1, except that the amount of acrylic acid in the pre-emulsion for dropping in Emulsion Production Example 1 was changed to 30 parts and the amount of cyclohexyl methacrylate was changed to 45 parts. The resin emulsion particles 11 had a Tg of −20° C. and an average particle size of 400 nm.

[0154] Emulsion Production Example 12 Emulsion 12 containing resin emulsion particles 12 was obtained in the same manner as in Emulsion Production Example 1, except that the amount of acrylic acid in the pre-emulsion for dropping in Emulsion Production Example 1 was changed to 0 parts, the amount of cyclohexyl methacrylate was changed to 75 parts, and no ammonia water was added. The resin emulsion particles 12 had a Tg of −21° C. and an average particle size of 190 nm.

[0155] Emulsion Production Example 13 Emulsion 13 containing resin emulsion particles 13 was obtained in the same manner as in Emulsion Production Example 1, except that a 5% aqueous solution of Adeka Reasoap SR-10 (manufactured by ADEKA Corporation) was used as the emulsifier instead of the 25% aqueous solution of Adeka Reasoap ER-20 in the pre-emulsion for dropping in Emulsion Production Example 1. The Tg of the emulsion particles 13 was −22° C. and the average particle size was 200 nm.

[0156]

[0157] Table 1 shows the amount of each component when the total amount of the monomer components used in each emulsion production example is taken as 100 parts, as well as the average particle size and Tg of the resulting emulsion particles. In Table 1, each symbol represents the following component. 2EHA 2-ethylhexyl acrylate CHMA cyclohexyl methacrylate HEMA hydroxyethyl methacrylate MMA methyl methacrylate BA n-butyl acrylate AA acrylic acid MAA methacrylic acid St styrene DVB divinylbenzene KBM-503 KBM-503 (Shin-Etsu Chemical Co., Ltd.) ER-20 ADEKA REASOAP ER-20 (ADEKA Corporation) RN-10 AQUALON RN-10 (Dai-ichi Kogyo Seiyaku Co., Ltd.) Newcol 723 Newcol 723 (Nippon Nyukazai Co., Ltd.) SR-10 ADEKA REASOAP SR-10 (ADEKA Corporation) V-50 V-50 (Fujifilm Wako Pure Chemical Industries, Ltd.) APS ammonium persulfate

[0158] <Pigment Dispersion Production Examples> [Pigment Dispersion Production Example 1] 5 parts of a dispersant, Discoat N-14 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 6 parts of propylene glycol, 70 parts of deionized water, 100 parts of titanium oxide, CR-95 (manufactured by Ishihara Sangyo Kaisha, Ltd.), and zirconia beads with a particle size of 0.5 mm were filled to a volume ratio of 50%, dispersed using a bead mill, and filtered through a 1 μm pore filter (MCP-1-C10S, manufactured by Advantec Co., Ltd.), thereby obtaining a white pigment dispersion containing 55% pigment. The average particle size of the pigment in the obtained white pigment dispersion was 330 nm.

[0159] <Inkjet Textile Printing White Ink Production Examples> [White Ink A Production Example] 23 parts (7 parts as resin emulsion particles) of Takelac WS-6021 (manufactured by Mitsui Chemicals, Inc., solids content 30%) as a urethane resin emulsion (resin emulsion particles: polyurethane), 25 parts (14 parts as pigment) of the white pigment dispersion obtained in Pigment Dispersion Production Example 1, 15 parts of triethylene glycol, 3 parts of diethylene glycol monobutyl ether, 0.3 parts of a surfactant KF-6011 (manufactured by Shin-Etsu Chemical Co., Ltd.), and deionized water were added to make a total of 100 parts. These ingredients were mixed and filtered through a 1 μm pore size filter (MCP-1-C10S manufactured by Advantec Co., Ltd.), to produce White Ink A.

[0160] [White Ink B Production Example] 29 parts (10 parts as resin emulsion particles) of Emulsion 13 (acrylic resin emulsion) obtained in Emulsion Production Example 13, 25 parts (14 parts as pigment) of the white pigment dispersion obtained in Pigment Dispersion Production Example 1, 15 parts of triethylene glycol, 3.0 parts of diethylene glycol monobutyl ether, and 0.3 parts of surfactant KF-6011 (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and filtered through a 1 μm pore size filter (MCP-1-C10S, manufactured by Advantec Co., Ltd.) to produce White Ink B.

[0161]

[0162] Examples Example 1 Preparation of Pretreatment Liquid A pretreatment liquid (1) was prepared by mixing 9 parts of emulsion 1 (3 parts as resin emulsion particles 1), 12.5 parts (5 parts as solids) of an aqueous calcium chloride solution (manufactured by Tokuyama Corporation, solids content 40%), 0.24 parts (0.06 parts as solids) of Epocross WS-700 (manufactured by Nippon Shokubai Co., Ltd., solids content 25%), 15 parts of diethylene glycol, and 63 parts of deionized water, and filtering the mixture through a 1 μm pore size filter (MCP-1-C10S, manufactured by Advantec Co., Ltd.).

[0163] (Pretreatment step) The pretreatment liquid (1) obtained above was added to a substrate at a concentration of 0.03 g / cm 3 The solution was applied to an A4-sized area of ​​a cotton fabric (a 100% cotton black T-shirt manufactured by Hanes Co., Ltd.) using a commercially available sprayer (DAHLIA#30 manufactured by Maruhachi Sangyo Co., Ltd.) so that the amount of the solution applied was 1. The fabric was then dried by heating at 165°C for 30 seconds using a manual heat press (TP630M manufactured by Horizon International Co., Ltd.) to obtain pretreated fabric (1).

[0164] (Image Forming Process by Inkjet Method) White ink A produced in the Inkjet Printing White Ink Production Example was introduced into a Mastermind MMP-TX13 textile printer, and an image was formed by the inkjet method. A 120 mm x 120 mm solid print was performed with the white ink on the pretreatment liquid-coated surface of the pretreated fabric (1) at 1440 dpi x 1440 dpi, a printing speed setting of 8, and an image was formed on the fabric. The fabric on which the image was formed was subjected to a heat treatment for 3 minutes in a hot air dryer at 150°C, to obtain a printed fabric (1) with an image printed thereon.

[0165] Examples 2 to 18 and Comparative Examples 1 to 6 Pretreatment liquids (2) to (18) for Examples 2 to 18 and pretreatment liquids (c1) to (c6) for Comparative Examples 1 to 6 were prepared in the same manner as in Example 1, except that the types and amounts of each raw material in the preparation of the pretreatment liquid in Example 1 were changed as shown in Tables 3 and 4, and the amount of deionized water was adjusted so that the total amount was 100 parts. Next, fabric pretreatment was performed in the same manner as in Example 1 using each pretreatment liquid of each Example and Comparative Example. Furthermore, image formation was performed by the inkjet method in the same manner as in Example 1, except that the white ink used was changed as shown in Tables 3 and 4, and printed textiles (2) to (18) and printed textiles (c1) to (c6) on which each image was formed were obtained. Tables 3 and 4 show the evaluation results for the pretreatment liquids prepared in each Example and Comparative Example and the printed textiles on which images were printed.

[0166]

[0167]

[0168] The ink-jet printing pretreatment liquid of the present invention is extremely useful as a pretreatment liquid for ink-jet printing because it has excellent storage stability and can give printed products with excellent color development and wet rub fastness.

Claims

1. A pretreatment liquid for inkjet textile printing, comprising a water-soluble polyvalent metal salt, resin emulsion particles, an oxazoline group-containing compound, and an aqueous medium, wherein the resin emulsion particles contain a nonionic emulsifier, a resin constituting the resin emulsion particles contains a structural unit having a carboxy group and / or a salt thereof, and the content of the structural unit having a carboxy group and / or a salt thereof in the resin is 0.1 to 2 mass %.

2. The ink-jet textile printing pretreatment liquid according to claim 1, wherein the nonionic emulsifier is a reactive emulsifier.

3. The ink-jet textile printing pretreatment liquid according to claim 1, wherein the resin constituting the resin emulsion particles contains a structural unit derived from an internally crosslinking monomer.

4. The ink-jet textile printing pretreatment liquid according to claim 1, wherein the aqueous medium contains water and a water-soluble organic solvent, and the water-soluble organic solvent contains a glycol.

5. The ink-jet textile printing pretreatment liquid according to claim 1, wherein the resin constituting the resin emulsion particles contains a structural unit derived from a styrene-based monomer.

6. The ink-jet textile printing pretreatment liquid according to claim 1, wherein the water-soluble polyvalent metal salt is an alkaline earth metal salt.

7. The ink-jet textile printing pretreatment liquid according to claim 1, wherein the anion constituting the water-soluble polyvalent metal salt is a chloride ion.

8. The ink-jet textile printing pretreatment liquid according to claim 1, wherein the resin constituting the resin emulsion particles contains a structural unit derived from a hydroxyl group-containing (meth)acrylic ester.

9. The pretreatment liquid for inkjet textile printing according to claim 1, wherein the resin constituting the resin emulsion particles comprises a structural unit having a carboxy group and / or a salt thereof; a structural unit derived from an alkyl (meth)acrylate ester having a homopolymer glass transition temperature of 0°C or lower; a structural unit derived from an alkyl (meth)acrylate ester and / or a structural unit derived from a styrene-based monomer having a homopolymer glass transition temperature of more than 0°C; and a structural unit derived from a hydroxyl group-containing (meth)acrylic ester.

10. A fabric to which the pretreatment liquid according to any one of claims 1 to 9 has been applied.

11. A printed item comprising a fabric having the solid matter of the pretreatment liquid according to any one of claims 1 to 9 adhered to its surface, and ink adhered to the solid matter.

12. A method for treating a fabric with the pretreatment liquid according to any one of claims 1 to 9, and then carrying out ink-jet printing.

13. A method for producing a printed textile, comprising: a pretreatment step of applying the pretreatment liquid according to any one of claims 1 to 9 to a fabric; and an image forming step of applying ink by an inkjet method to the treated surface of the fabric obtained in the pretreatment step to form an image.

Images