Adhesive ink and method for producing printed material using said adhesive ink

Abstract

The present invention addresses the problem of providing an adhesive ink that has excellent transferability during transfer printing on fabric and that can improve the wet abrasion fastness and feel of the obtained printed material.　The problem can be solved by an adhesive ink that contains a resin, a water-soluble organic solvent, and water, the resin having a glass transition temperature of 30°C or less and a weight-average molecular weight of 10,000-700,000.

Description

[Technical Field]

[0001] The present invention relates to an adhesive ink, an ink set containing the adhesive ink, a transfer medium containing the adhesive ink, and a printed item transfer-printed using the adhesive ink. [Background technology]

[0002] Conventionally, there has been known a method of transferring and printing characters or images formed by printing colored inks on a transfer substrate onto a transfer medium. For example, Patent Document 1 describes that excellent transferability to a transfer medium such as plastic is achieved by using a transfer medium obtained by a method including a colored layer forming step of ejecting ink from an inkjet head toward a substrate to form a colored layer on the substrate, and an adhesive layer forming step of ejecting an adhesive liquid from an inkjet head toward the colored layer to form an adhesive layer on the colored layer.

[0003] Furthermore, Patent Document 2 describes an aqueous hot melt adhesive ink for digital textile printing, and states that by adjusting the amounts of aqueous hot melt adhesive resin, aqueous curing agent, humectant, surfactant, antifoaming agent, bactericidal preservative, pH adjuster, and deionized water, it is possible to provide an adhesive ink that is applicable to inkjet printing work and has good adhesive strength, water resistance, and flexibility. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-126026 [Patent Document 2] Chinese Patent Application Publication No. 111117360 Summary of the Invention [Problem to be solved by the invention]

[0005] In transfer printing, not only is excellent transferability required, but when the transfer medium is fabric, the resulting printed product (transfer-printed fabric) is also required to have good wet rub fastness and texture. However, Patent Document 1 does not consider at all aspects in which the transfer medium is fabric. Furthermore, Patent Document 2 describes transfer printing in which the transfer medium is fabric, but does not sufficiently consider transferability, wet rub fastness, and texture.

[0006] Therefore, an object of the present invention is to provide an adhesive ink, an ink set, and a transfer medium that have excellent transferability when transferred onto fabrics and can improve the wet rub fastness and texture of the resulting printed textile. [Means for solving the problem]

[0007] As a result of extensive research to solve the above problems, the present inventors have discovered that by adjusting the balance between the glass transition temperature and weight average molecular weight of the resin contained in the adhesive ink, it is possible to achieve excellent transferability during transfer printing onto fabrics and to improve the wet rub fastness and texture of the resulting printed textile, and have thus completed the present invention.

[0008] That is, the present invention is as follows. [1] An inkjet adhesive ink used for transfer printing on fabric, the adhesive ink contains a resin, a water-soluble organic solvent, and water; The resin in the adhesive ink has a glass transition temperature of 30° C. or lower and a weight average molecular weight of 10,000 to 700,000. [2] The adhesive ink according to [1], wherein the resin comprises at least one selected from the group consisting of acrylic resins and polyester resins. [3] The adhesive ink according to [1] or [2], wherein the resin is contained in the adhesive ink as emulsion particles. [4] The adhesive ink according to any one of [1] to [3], wherein the fabric is formed from cotton, polyester fiber, polypropylene fiber, nylon fiber, or a mixture thereof. [5] The adhesive ink according to any one of [1] to [4], and a colored ink containing a pigment and a resin. [6] The resin contained in the adhesive ink includes at least one resin selected from the group consisting of an acrylic resin and a polyester resin, The ink set according to [5], wherein the resin contained in the color inks includes at least one resin selected from the group consisting of acrylic resins and polyester resins. [7] A transfer medium in which the adhesive ink according to any one of [1] to [4] is printed on a transfer substrate, with or without a colored ink layer formed from a colored ink containing a pigment and a resin. [8] The transfer medium according to [7], wherein the transfer substrate is a plastic film or paper. [9] The transfer medium according to [7] or [8], further comprising an ink-receiving layer on the surface of the transfer substrate on which the adhesive ink is printed.

[10] A printed item that is transfer printed using the adhesive ink according to any one of [1] to [4].

[11] Step 3: Printing an adhesive ink by inkjet onto a transfer substrate or onto a colored ink layer laminated on the transfer substrate; and Step 4: drying the adhesive ink; The adhesive ink used in step 3 contains a resin, a water-soluble organic solvent, and water, and the resin has a glass transition temperature of 30°C or lower and a weight average molecular weight of 10,000 to 700,000. A method for manufacturing a transfer medium for transfer printing onto fabric.

[12] The manufacturing method according to

[11] , wherein the resin contained in the adhesive ink includes at least one resin selected from the group consisting of acrylic resins and polyester resins.

[13] The step 3 is a step of printing an adhesive ink by inkjet printing onto a colored ink layer laminated on a transfer substrate, The manufacturing method according to

[11] or

[12] , wherein the color ink layer is formed by step 1 of printing color inks on a transfer substrate by inkjet printing, and step 2 of drying the color inks.

[14] The manufacturing method according to

[13] , wherein the color ink contains a pigment and a resin.

[15] The resin contained in the adhesive ink includes at least one resin selected from the group consisting of an acrylic resin and a polyester resin, The manufacturing method according to

[14] , wherein the resin contained in the color ink includes at least one selected from the group consisting of acrylic resins and polyester resins.

[16] The manufacturing method according to any one of

[13] to

[15] , wherein the step 2 is a step of evaporating 20 to 80 mass % of 100 mass % of the components of the color ink excluding the solid content.

[17] The manufacturing method according to any one of

[11] to

[16] , wherein the thickness of the adhesive ink after the drying step 4 is 0.5 to 200 μm.

[18] The manufacturing method according to any one of

[11] to

[17] , wherein the resin contained in the adhesive ink is contained in the adhesive ink as emulsion particles.

[19] The method according to any one of

[11] to

[18] , wherein the transfer substrate is a plastic film or paper.

[20] The manufacturing method according to any one of

[11] to

[19] , wherein the printing of the adhesive ink in step 3 is carried out on (I) an ink-receiving layer laminated on a transfer substrate, or (II) the colored ink layer side of a laminate in which a transfer substrate, an ink-receiving layer, and a colored ink layer are laminated in this order.

[21] A method for producing a printed textile, comprising a step of transferring and printing onto a fabric the transfer medium obtained by the production method according to any one of

[11] to

[20] .

[22] The transfer printing step includes a contact step of bringing the surface of the transfer medium, on which the adhesive ink is printed, into close contact with the fabric while facing the fabric, and a step of peeling the transfer substrate from the fabric,

[21] The manufacturing method according to

[21] , wherein the adhesion time in the adhesion step is 30 seconds or less.

[23] The manufacturing method according to

[21] or

[22] , wherein the fabric is formed from cotton, polyester fiber, polypropylene fiber, nylon fiber, or a mixture thereof. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide an adhesive ink that has excellent transferability when transferred onto fabrics during transfer printing and can improve the wet rub fastness and texture of the resulting printed textile. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a schematic cross-sectional view showing an example of a layered structure of a transfer medium according to the present invention. [Figure 2] FIG. 10 is a schematic cross-sectional view showing another example of the layered structure of the transfer medium of the present invention. [Figure 3] FIG. 10 is a schematic cross-sectional view showing yet another example of the layered structure of the transfer medium of the present invention. [Figure 4] 1 is a schematic cross-sectional view showing an example of a laminated structure of a transfer medium and a fabric during transfer printing of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] 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 "greater than or equal to A and less than or equal to B." 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." Furthermore, a "structural unit derived from" corresponds to a structure in which the ethylenically unsaturated double bond of each monomer component is opened (a structure in which the double bond (C=C) becomes a single bond (-C-C-)).

[0012] 1. Adhesive ink The adhesive ink of the present invention is an inkjet adhesive ink used for transfer printing onto fabric, and is characterized in that it contains a resin, a water-soluble organic solvent, and water, and the resin has a glass transition temperature of 30°C or less and a weight average molecular weight of 10,000 to 700,000. The adhesive ink of the present invention can also contain other components in addition to the components described above, as necessary. Each component constituting the adhesive ink of the present invention will be described below.

[0013] <Resin> The adhesive ink of the present invention contains a resin, and the resin may be used alone or in combination of two or more types.

[0014] The glass transition temperature (Tg) of the resin contained in the adhesive ink of the present invention is 30°C or lower, preferably 20°C or lower, more preferably 15°C or lower, and even more preferably 10°C or lower. By adjusting the Tg of the resin within the above range, the texture of the resulting printed textile is excellent. Furthermore, by adjusting the Tg of the resin within the above range and the weight-average molecular weight of the resin to 10,000 to 700,000, the transferability during transfer printing and the wet rub fastness of the resulting printed textile are excellent. The lower limit of the Tg of the resin is, for example, −50°C or higher, preferably −30°C or higher, more preferably −20°C or higher, and even more preferably −10°C or higher. Transfer media may be wound into a roll for storage, and in this case, blocking by the adhesive ink may become a problem. By adjusting the lower limit of the Tg of the resin within the above range, such blocking can be suppressed. That is, the Tg of the resin is preferably from -50 to 30°C, more preferably from -30 to 20°C, even more preferably from -20 to 15°C, and particularly preferably from -10 to 10°C.

[0015] The Tg of a resin can be determined by differential scanning calorimetry (DSC). Specifically, for example, a differential scanning calorimetry analyzer (NETZSCH "DSC 3500") is used to heat and cool the resin in the following steps to create a DSC curve, and the midpoint glass transition temperature determined from the DSC curve during the second heating cycle is taken as the glass transition temperature (Tg) of the resin. (Step 1) The temperature is increased from -50°C to 150°C at a rate of 10°C / min and held at 150°C for 5 minutes. (Step 2) The temperature is decreased from 150°C to -50°C at a rate of 10°C / min and held at -50°C for 5 minutes. (Step 3) The temperature is increased from -50°C to 150°C at a rate of 10°C / min.

[0016] When the resin has a core-shell structure, multiple glass transition temperatures may be observed. In this case, it is sufficient that any one of the glass transition temperatures satisfies the above range, and it is preferable that all of the glass transition temperatures satisfy the above range. Furthermore, when two or more resins are used, it is preferable that the Tg of the resin that is the main component satisfies the above range, and it is more preferable that the Tg of each of all the resins is within the above range. Note that the term "main component resin" refers to a resin that preferably accounts for 50% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, of the total 100% by mass of the resins contained in the adhesive ink.

[0017] The weight-average molecular weight of the resin contained in the adhesive ink of the present invention is 10,000 or more, preferably 20,000 or more, and may be 30,000 or more, or 50,000 or more. By adjusting the weight-average molecular weight of the resin within the above range, it is possible to prevent the adhesive ink from flowing after printing. Furthermore, the weight-average molecular weight of the resin is 700,000 or less, preferably 500,000 or less, more preferably 400,000 or less, and may be 350,000 or less, or 300,000 or less. By adjusting the weight-average molecular weight of the resin within the above range and adjusting the Tg of the resin to 30°C or less, the transferability during transfer printing and the wet rub fastness of the resulting textile print are excellent. That is, the weight average molecular weight of the resin is 10,000 to 700,000, preferably 20,000 to 500,000, more preferably 20,000 to 400,000, and may be 30,000 to 350,000 or 50,000 to 300,000.

[0018] The weight-average molecular weight of the resin can be calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). Specifically, for example, a resin solution dissolved in tetrahydrofuran (THF) to a concentration of 0.2% by mass is used as a sample, and the weight-average molecular weight (polystyrene conversion) can be calculated from a chart prepared using gel permeation chromatography (manufactured by Tosoh Corporation, product number: HLC-8320GPC, column: TSK-GEL SuperMultiporeHZ, eluent: THF) and a calibration curve prepared using standard polystyrene manufactured by Tosoh Corporation.

[0019] When two or more resins are used, it is sufficient that the weight average molecular weight of the resins as a mixture falls within the above range, but it is preferable that the weight average molecular weights of all the resins fall within the above range.

[0020] The type of resin contained in the adhesive ink of the present invention is not particularly limited, and examples thereof include vinyl resins, acrylic resins, polyester resins, olefin resins, urethane resins, fluorine resins, silicone resins, epoxy resins, phenoxy resins, phenol resins, and xylene resins, with acrylic resins and / or polyester resins being preferred. In particular, from the viewpoint of suppressing yellowing of the resulting adhesive ink layer, it is preferable to use an acrylic resin as the resin. The adhesive ink may be heated as described below in the production of transfer media or printed textiles, and the resulting adhesive ink layer may turn yellow due to this heating. Suppression of such yellowing is sometimes required to improve the design of the resulting printed textile, and the use of an acrylic resin as the resin can suppress the above-mentioned yellowing.

[0021] The acrylic resin is a resin containing structural units derived from (meth)acrylic monomers. The content of the structural units derived from (meth)acrylic monomers relative to the total (100% by mass) of structural units derived from all monomer components constituting the acrylic resin is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and may be 70 or 85% by mass or more, or may be 100% by mass or 90% by mass or less. That is, the content is preferably 20 to 100% by mass, more preferably 30 to 100% by mass, even more preferably 40 to 100% by mass, and may be 70 to 100% by mass or 85 to 90% by mass. By adjusting the content of the structural units derived from (meth)acrylic monomers within the above range, the wet rub fastness of the resulting printed textile is further improved, and yellowing of the adhesive ink layer in the printed textile tends to be further suppressed.

[0022] Examples of the (meth)acrylic monomer include monofunctional (meth)acrylates and polyfunctional (meth)acrylates.

[0023] Examples of the monofunctional (meth)acrylate include: (Meth)acrylic acid, salts of (meth)acrylic acid (hereinafter collectively referred to as (meth)acrylic acid (salts)); alkyl (meth)acrylates such as linear alkyl (meth)acrylates (e.g., methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, 2-octyl (meth)acrylate, tridecyl (meth)acrylate, n-lauryl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate), and cyclic alkyl (meth)acrylates (e.g., cyclohexyl (meth)acrylate and isobornyl (meth)acrylate); 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; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate and α-methylglycidyl (meth)acrylate; alkoxyalkyl group-containing (meth)acrylates such as methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, and trimethylolpropane tripropoxy (meth)acrylate; silyl group-containing (meth)acrylates such as γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropylhydroxysilane, and γ-(meth)acryloyloxypropylmethylhydroxysilane; 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; (meth)acrylates containing an aziridinyl group, such as (meth)acryloylaziridine and 2-aziridinylethyl (meth)acrylate; oxo group-containing (meth)acrylates such as (di)ethylene glycol (methoxy) (meth)acrylates such as ethylene glycol (meth)acrylate, ethylene glycol methoxy (meth)acrylate, diethylene glycol (meth)acrylate, and diethylene glycol methoxy (meth)acrylate; Examples include piperidine group-containing (meth)acrylates such as 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine and 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine; and the like, and one or more of these can be selected and used.

[0024] Examples of the salt of (meth)acrylic acid include alkali metal salts of (meth)acrylic acid and ammonium salts of (meth)acrylic acid. Examples of the alkali metal constituting the alkali metal salt include lithium, sodium, and potassium. The ammonium salt is NH4 + The organic ammonium may be tetraalkylammonium (preferably tetra C) such as tetramethylammonium or tetrabutylammonium. 1-10alkylammonium), trialkylammonium (preferably triC) such as trimethylammonium, triethylammonium, and tributylammonium 1-10 hydroxyalkylammonium (preferably mono-, di- or tri(hydroxy C alkyl ammonium), monoethanolammonium, diethanolammonium, triethanolammonium, etc. 1-10 alkyl)ammonium), dialkylmonohydroxyalkylammonium (preferably diC 1-10 Alkyl mono(hydroxy C 1-10 alkyl)ammonium) and the like.

[0025] Among these, the monofunctional (meth)acrylate preferably contains (meth)acrylic acid (salt) and / or alkyl (meth)acrylate, more preferably contains at least alkyl (meth)acrylate, and further preferably contains (meth)acrylic acid (salt) and alkyl (meth)acrylate.

[0026] The content of the structural units derived from (meth)acrylic acid (salts) relative to 100 parts by mass of the structural units derived from alkyl (meth)acrylate is preferably 0 to 3 parts by mass, more preferably 0 to 1 part by mass, even more preferably 0 to 0.5 parts by mass, still more preferably 0.1 to 0.5 parts by mass, and particularly preferably 0.3 to 0.5 parts by mass. By adjusting the content of the structural units derived from (meth)acrylic acid (salts) within the above range, the washing fastness of the obtained printed textile tends to be improved.

[0027] The alkyl (meth)acrylate is an alkyl (meth)acrylate having an alkyl group with 1 to 18 carbon atoms (hereinafter referred to as C 1-18 It is preferable that the compound contains alkyl (meth)acrylate, 4-12 It is more preferable that the alkyl (meth)acrylate is contained. It is also preferable to use two or more alkyl (meth)acrylates having different carbon numbers in combination. For example, C 1-3 Alkyl (meth)acrylate and C4-18 Form in which alkyl (meth)acrylate is used in combination, C 4-6 Alkyl (meth)acrylate and C 7-18 Form in which alkyl (meth)acrylate is used in combination, C 1-3 Alkyl (meth)acrylate and C 4-6 Alkyl (meth)acrylate and C 7-18 and a form in which alkyl (meth)acrylate is used in combination.

[0028] The content of structural units derived from monofunctional (meth)acrylates (preferably the total content of structural units derived from (meth)acrylic acid (salt) and structural units derived from alkyl (meth)acrylates) relative to the total 100% by mass of structural units derived from all monomer components constituting the acrylic resin is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and may be 70% by mass or more or 80% by mass or more, or may be 100% by mass or 90% by mass or less. That is, the content is preferably 20 to 100% by mass, more preferably 30 to 100% by mass, even more preferably 40 to 100% by mass, and may be 70 to 100% by mass or 80 to 90% by mass.

[0029] Examples of the polyfunctional (meth)acrylate include: di(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms, such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene 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; polyalkylene glycol di(meth)acrylates having an added mole number of alkylene oxide groups having 2 to 4 carbon atoms of 2 to 50, such as polyethylene glycol di(meth)acrylate having an added mole number of ethylene oxide of 2 to 50, polypropylene glycol di(meth)acrylate having an added mole number of propylene oxide of 2 to 50, and tripropylene glycol di(meth)acrylate; Tri(meth)acrylates of polyhydric 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, pentaerythritol monohydroxytri(meth)acrylate, and trimethylolpropane triethoxytri(meth)acrylate; tetra(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms, such as pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate; Penta(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms, such as pentaerythritol penta(meth)acrylate and dipentaerythritol (monohydroxy)penta(meth)acrylate; Hexa(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms, such as pentaerythritol hexa(meth)acrylate; Epoxy group-containing (meth)acrylates such as bisphenol A di(meth)acrylate, 2-(2'-vinyloxyethoxyethyl)(meth)acrylate, and epoxy (meth)acrylate; Polyfunctional (meth)acrylates such as urethane (meth)acrylate; etc., and one or more of these may be selected and used.

[0030] The content of structural units derived from polyfunctional (meth)acrylates relative to the total of structural units derived from all monomer components constituting the acrylic resin (100% by mass) is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0031] The acrylic resin preferably has a structural unit derived from an acid group-containing monomer. When the acrylic resin contains a structural unit derived from an acid group-containing monomer, the stability of the acrylic resin is improved. The structural unit derived from the acid group-containing monomer may be contained in the acrylic resin alone or in combination of two or more types.

[0032] The acid group-containing monomer may have at least one acid group and at least one polymerizable unsaturated group in the molecule. Examples of the acid group include a sulfo group, a carboxy group, and salts thereof, with a carboxy group or a salt thereof being preferred. The acid group-containing monomer may be the above-mentioned (meth)acrylic acid (salt) or another acid group-containing monomer. Specific examples of the acid group-containing monomer include unsaturated monocarboxylic acids or salts thereof, such as (meth)acrylic acid, cinnamic acid, and crotonic acid; unsaturated dicarboxylic acids or salts thereof, such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; unsaturated dicarboxylic acid monoesters or salts thereof, such as maleic acid monomethyl ester, maleic acid monobutyl ester, itaconic acid monomethyl ester, and itaconic acid monobutyl ester; unsaturated dicarboxylic acid anhydrides, such as maleic anhydride; 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and 2-acryloyloxyethyl hexahydrophthalic acid. Examples of the salt include alkali metal salts and ammonium salts, and specific examples of the alkali metal atom and ammonium constituting the salt are the same as those described above. Among these, the acid group-containing monomer is preferably an unsaturated monocarboxylic acid and / or a salt thereof, and more preferably (meth)acrylic acid (salt).

[0033] When the acrylic resin contains structural units derived from acid group-containing monomers, the content of structural units derived from acid group-containing monomers (preferably the content of structural units derived from (meth)acrylic acid (salts)) relative to the total 100% by mass of structural units derived from all monomer components constituting the acrylic resin is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. That is, the content is preferably 0.1 to 5% by mass, more preferably 0.3 to 4% by mass, even more preferably 0.5 to 3% by mass, and still more preferably 1.0 to 3% by mass. From the viewpoint of improving the washing fastness of the resulting printed textile, the content of structural units derived from acid group-containing monomers (preferably the content of structural units derived from (meth)acrylic acid (salts)) relative to the total of structural units derived from all monomer components constituting the acrylic resin (100% by mass) is preferably 0 to 3% by mass, more preferably 0 to 1% by mass, even more preferably 0 to 0.5% by mass, still more preferably 0.1 to 0.5% by mass, and particularly preferably 0.3 to 0.5% by mass.

[0034] The acrylic resin may further have a structural unit derived from a styrene-based monomer. The total content of the structural units derived from a (meth)acrylic monomer and the structural units derived from a styrene-based monomer (preferably the total content of the structural units derived from (meth)acrylic acid (salt), the structural units derived from an alkyl (meth)acrylate, and the structures derived from a styrene-based monomer) relative to the total 100% by mass of the structural units derived from all monomer components constituting the acrylic resin is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 95% by mass or more, and may be 100% by mass.

[0035] Examples of the styrene-based monomer include styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, vinyltoluene, 2-styrylethyltrimethoxysilane, and divinylbenzene, and one or more of these may be selected and used. The styrene-based monomer may have a functional group, such as an alkyl group (e.g., a methyl group or a tert-butyl group), a nitro group, a nitrile group, an alkoxyl group, an acyl group, a sulfone group, a hydroxyl group, or a halogen atom, present on the benzene ring constituting the styrene-based monomer. Among the styrene-based monomers, styrene is preferred from the viewpoint of improving water resistance.

[0036] The content of structural units derived from styrene-based monomers relative to the total 100% by mass of structural units derived from all monomer components constituting the acrylic resin may be, for example, 10% by mass or more, or 30% by mass or more, and is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. That is, the content is preferably 0 to 80% by mass, or may be 10 to 70% by mass, or 30 to 60% by mass.

[0037] In particular, the acrylic resin contains a styrene-based monomer and / or C 1-3 A structural unit derived from a chain alkyl methacrylate and C 4-12 and a structural unit derived from a chain alkyl acrylate, 1-3 A structural unit derived from a chain alkyl methacrylate and C 4-12 It is more preferable that the copolymer contains a structural unit derived from a chain alkyl acrylate. In addition to these structural units, it is even more preferable that the copolymer further contains a structural unit derived from an acid group-containing monomer (preferably, (meth)acrylic acid (salt)). Styrene-based monomers, C, and acrylic resins, based on 100% by mass of structural units derived from all monomer components constituting the acrylic resin. 1-3 Chain alkyl methacrylate, C 4-12The total content of the structural units derived from the chain alkyl acrylate and the acid group-containing monomer is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and may be 100% by mass. C relative to 100% by mass of the total structural units derived from all monomer components that make up the acrylic resin 4-12 The content of structural units derived from chain alkyl acrylate may be adjusted appropriately depending on the target Tg, but is preferably 20 to 90 mass %, more preferably 30 to 75 mass %, and even more preferably 40 to 60 mass %. Styrene-based monomers and C 1-3 The total content of structural units derived from chain alkyl methacrylate is C 4-12 The amount is preferably 20 to 200 parts by mass, more preferably 50 to 150 parts by mass, and even more preferably 80 to 120 parts by mass, relative to 100 parts by mass of the structural unit derived from the chain alkyl acrylate. The content of structural units derived from acid group-containing monomers is 1-3 Chain alkyl methacrylate, and C 4-12 The amount is preferably 0 to 3 parts by mass, more preferably 0.1 to 1 part by mass, and even more preferably 0.3 to 0.5 parts by mass, relative to 100 parts by mass of the total of structural units derived from chain alkyl acrylate.

[0038] The acrylic resin may further have one or more structural units derived from monomers other than (meth)acrylic monomers, acid group-containing monomers and styrene monomers (hereinafter sometimes referred to as other monomers).

[0039] The other monomer is not particularly limited as long as it has at least one polymerizable unsaturated group in the molecule, and examples thereof include 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; vinyl monomers such as vinyl acetate, vinyl chloride, and vinyl benzoate; acrylonitrile; (meth)acrylamide-based monomers such as (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, and N,N-dimethyl(meth)acrylamide; and olefin-based monomers such as ethylene and propylene.

[0040] The acrylic resin can be produced by a conventionally known polymerization method, such as solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization. Among these, emulsion polymerization is preferred. That is, the acrylic resin can be produced by emulsion polymerization of the aforementioned monomer components ((meth)acrylic monomers, and optionally styrene-based monomers, acid group-containing monomers, and other monomers) in an aqueous solvent in the presence of an emulsifier and a polymerization initiator. In this specification, the term "monomer component" refers to a compound having at least one polymerizable unsaturated group in the molecule, other than the reactive emulsifiers described below. The specific means and conditions for emulsion polymerization can be appropriately selected and adopted from the means and techniques used in conventionally known emulsion polymerization methods.

[0041] The emulsifier used in the emulsion polymerization is not limited, but includes nonionic emulsifiers, anionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, polymeric emulsifiers, etc., and conventionally known emulsifiers can be used. These emulsifiers may be used alone or in combination of two or more. Among the emulsifiers, nonionic emulsifiers and / or anionic emulsifiers are preferred. Emulsifiers containing polymerizable groups in the molecule (hereinafter sometimes referred to as reactive emulsifiers) are also preferred. Among the emulsifiers, nonionic emulsifiers containing polymerizable groups or anionic emulsifiers containing polymerizable groups are particularly preferred. The amount of reactive emulsifier in 100% by mass of the emulsifier used in the emulsion polymerization is not particularly limited, but is, for example, 10 to 80% by mass, preferably 30 to 60% by mass.

[0042] Examples of anionic emulsifiers include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate and sodium alkyl diphenyl ether disulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; polyoxyethylene alkyl sulfonate salts; polyoxyethylene alkyl ether sulfate salts; polyoxyethylene alkyl aryl ether sulfate salts; dialkyl sulfosuccinate salts; and aryl sulfonic acid-formalin. condensates; fatty acid salts such as ammonium laurate and sodium stearylate; sulfates or salts thereof having an allyl group such as bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salts, propenyl-alkyl sulfosuccinate ester salts, (meth)acrylic acid polyoxyethylene sulfonate salts, (meth)acrylic acid polyoxyethylene phosphonate salts, and sulfonate salts of allyloxymethyl alkyloxy polyoxyethylene; sulfate ester salts of allyloxymethyl alkoxyethyl polyoxyethylene; and polyoxyalkylene alkenyl ether ammonium sulfate salts; but the present invention is not limited to these examples.

[0043] Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, condensates of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, condensation products of ethylene oxide and aliphatic amines, and polyoxyalkylene alkenyl ethers, but are not limited to these examples.

[0044] Examples of polymeric emulsifiers include poly(meth)acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl(meth)acrylates such as polyhydroxyethyl acrylate; and copolymers containing one or more of the monomers that make up these polymers as copolymerization components, but are not limited to these examples.

[0045] In this specification, the reactive emulsifier refers to a compound having a polymerizable unsaturated group, a hydrophilic group, and a hydrophobic group, and the number of polymerizable unsaturated groups may be one or more. Examples of the polymerizable unsaturated group include groups having an ethylenically unsaturated double bond, and specific examples thereof include a (meth)acryloyl group, a vinyl group, an allyl group, and a styryl group. Examples of hydrophilic groups include groups known as emulsifiers (surfactants), and preferred examples include anionic groups such as sulfonic acid groups, phosphoric acid groups, sulfate ester residues, and phosphate ester residues; and nonionic groups such as polyether groups and ester groups. Examples of the hydrophobic group include groups known as 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 having a phenyl group), and polycyclic phenyl groups.

[0046] Examples of reactive emulsifiers include: Propenyl-alkyl sulfosuccinate salts, (meth)acrylic acid polyoxyethylene sulfonate salts, (meth)acrylic acid polyoxyethylene phosphonate salts (e.g., Sanyo Chemical Industries, Ltd., trade name: Eleminol RS-30, etc.), polyoxyethylene alkylpropenylphenyl ether sulfonate salts (e.g., Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10, etc.), sulfonate salts of allyloxymethyl alkyloxy polyoxyethylene (e.g., Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.), polyoxyethylene styrenated propenyl phenyl ether sulfate ester ammonium anionic emulsifiers having a polymerizable group, such as emulsifiers (e.g., trade name: Aqualon AR-10, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), sulfonate salts of allyloxymethylnonylphenoxyethyl hydroxypolyoxyethylene (e.g., trade name: Adeka Reasoap SE-10, manufactured by ADEKA Corporation), allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salts (e.g., trade name: Adeka Reasoap SR-10, SR-30, manufactured by ADEKA Corporation), and bis(polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salts (e.g., trade name: Antox MS-60, manufactured by Nippon Nyukazai Co., Ltd.); Nonionic emulsifiers having a polymerizable group such as polyoxyethylene styrenated propenyl phenyl ether (for example, trade name: Aqualon AN-10, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), allyloxymethyl alkoxyethyl hydroxypolyoxyethylene (for example, trade name: Adeka Reasop ER-20, manufactured by ADEKA Corporation), polyoxyethylene alkylpropenyl phenyl ether (for example, trade name: Aqualon RN-20, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene (for example, trade name: Adeka Reasop NE-10, manufactured by ADEKA Corporation), are included, but are not limited to these examples.

[0047] The amount of the emulsifier used is not limited, but is, for example, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1.0 to 5 parts by mass, relative to 100 parts by mass of the monomer component. If necessary, protective colloids can be used alone or together with the emulsifier. When a reactive emulsifier is used as the emulsifier, the polymerizable groups of the reactive emulsifier react during polymerization, resulting in the resulting resin having structural units derived from the reactive emulsifier. The content of the structural units derived from the reactive emulsifier in the polymer is preferably 0.1 to 8 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1.0 to 3 parts by mass, per 100 parts by mass of the structural units derived from the monomer components.

[0048] The polymerization initiator used in the emulsion polymerization includes, but is not limited to, azo-based polymerization 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); persulfates such as ammonium persulfate and potassium persulfate; and peroxide-based polymerization initiators such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide. These polymerization initiators may be used alone or in combination of two or more.

[0049] The amount of 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. If it is necessary to further increase the polymerization rate or lower the reaction temperature, a reducing agent such as a soluble sulfite (e.g., sodium bisulfite) or ascorbic acid, or a metal compound that generates heavy metal ions in water, such as ferrous sulfate, can be combined with the polymerization initiator to form a redox initiator.

[0050] In addition, to adjust the weight-average molecular weight of the resulting resin, the polymerization reaction may be carried out in the presence of a chain transfer agent. Examples of chain transfer agents include 2-ethylhexyl thioglycolate, tert-dodecyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid, 2-mercaptoethanol, α-methylstyrene, and α-methylstyrene dimer, but the present invention is not limited to these examples. These chain transfer agents may be used alone or in combination of two or more. The amount of chain transfer agent used may be adjusted appropriately depending on the target weight-average molecular weight, but is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the monomer components.

[0051] The reaction temperature and reaction time during the emulsion polymerization can be appropriately set taking into consideration the weight-average molecular weight of the target resin, the blending ratio of the monomer components, and the type of polymerization initiator. 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 preferably carried out under an inert gas atmosphere such as nitrogen gas.

[0052] Examples of aqueous solvents used in the emulsion polymerization include water and mixed solvents of water and water-soluble organic solvents. A water-soluble organic solvent refers to an organic solvent that dissolves in water at a concentration of 0.01% by mass or more at room temperature and normal pressure. In this specification, room temperature means 25°C, and normal pressure means 1 atmosphere. The water content in the aqueous solvent 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.

[0053] 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 1-4 alcohol); Dihydric alcohols (preferably glycols) such as propylene glycol, 1,3 propanediol, dipropylene glycol, tripropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; Trihydric alcohols such as glycerin; ethers of monoethylene glycol such as monoethylene glycol monomethyl ether, monoethylene glycol monoethyl ether, monoethylene glycol monopropyl ether, monoethylene glycol monoisopropyl ether, monoethylene glycol monobutyl ether, and monoethylene glycol monoisobutyl ether (preferably, monoalkyl ethers of monoethylene glycol); ethers of monopropylene glycol such as monopropylene glycol monomethyl ether, monopropylene glycol monoethyl ether, monopropylene glycol monopropyl ether, monopropylene glycol monoisopropyl ether, monopropylene glycol monobutyl ether, and monopropylene glycol monoisobutyl ether (preferably, monoalkyl ethers of monopropylene glycol); ethers of diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, and diethylene glycol monoisobutyl ether (preferably, monoalkyl ethers of diethylene glycol); ethers of dipropylene glycol such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, and dipropylene glycol monoisobutyl ether (preferably, monoalkyl ethers of dipropylene glycol); ethers of polyethylene glycol (preferably, monoalkyl ethers of polyethylene glycol), such as monomethyl ether of polyethylene glycol (number of moles of EO added=2 to 10, preferably 2 to 4), monoethyl ether of polyethylene glycol (number of moles of EO added=2 to 10, preferably 2 to 4), monopropyl ether of polyethylene glycol (number of moles of EO added=2 to 10, preferably 2 to 4), monoisopropyl ether of polyethylene glycol (number of moles of EO added=2 to 10, preferably 2 to 4), monobutyl ether of polyethylene glycol (number of moles of EO added=2 to 10, preferably 2 to 4), and monoisobutyl ether of polyethylene glycol (number of moles of EO added=2 to 10, preferably 2 to 4); ethers of polypropylene glycol (preferably monoalkyl ethers of polypropylene glycol), such as monomethyl ether of polypropylene glycol (number of moles of PO added=2 to 10, preferably 2 to 4), monoethyl ether of polypropylene glycol (number of moles of PO added=2 to 10, preferably 2 to 4), monopropyl ether of polypropylene glycol (number of moles of PO added=2 to 10, preferably 2 to 4), monoisopropyl ether of polypropylene glycol (number of moles of PO added=2 to 10, preferably 2 to 4), monobutyl ether of polypropylene glycol (number of moles of PO added=2 to 10, preferably 2 to 4), and monoisobutyl ether of polypropylene glycol (number of moles of PO added=2 to 10, preferably 2 to 4); Heterocycles such as 2-pyrrolidone and N-methyl-2-pyrrolidone; Ketones such as acetone and methyl ethyl ketone;

[0054] Among these, propylene glycol, glycerin, diethylene glycol, triethylene glycol, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, monobutyl ether of polyethylene glycol (EO addition mole number = 2 to 4), and 2-pyrrolidone are preferred. These water-soluble organic solvents may be used alone or in combination of two or more.

[0055] The amount of the aqueous solvent used when carrying out the emulsion polymerization is not limited, but is preferably 20 to 300 parts by mass, more preferably 30 to 200 parts by mass, and even more preferably 40 to 150 parts by mass, per 100 parts by mass of the monomer components.

[0056] Specific examples of the emulsion polymerization include monomer dropping polymerization, pre-emulsion dropping polymerization, seed polymerization, and multi-stage polymerization.

[0057] If necessary, an appropriate amount of additives such as a pH buffer, a chelating agent, etc. may be added to the reaction system in the emulsion polymerization. The amount of the additive varies depending on the type of additive and cannot be determined in general, but is usually preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the monomer components.

[0058] In such an emulsion polymerization method, an emulsion is obtained in which the acrylic resin is dispersed in the aqueous solvent as emulsion particles.

[0059] The polyester resin is not particularly limited as long as it is a polymer having an ester bond in the main chain, but is preferably a condensation polymer of an aromatic dicarboxylic acid and a diol compound.

[0060] Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid.

[0061] Examples of the diol compound include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, and neopentyl glycol; aromatic alcohols such as alkylene oxide adducts of bisphenol A, such as polyoxypropylene-2,2-bis(4-hydroxyphenyl)propane and polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane; and hydrogenated bisphenol A or its alkylene oxide (having 2 to 4 carbon atoms) (average number of moles added: 1 to 16) adducts.

[0062] An aliphatic polybasic acid may be added to the polyester resin to improve fluidity. Examples of the aliphatic polybasic acid include saturated aliphatic dicarboxylic acids or anhydrides thereof, such as succinic acid, succinic anhydride, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and 1,4-cyclohexanedicarboxylic acid; unsaturated aliphatic dicarboxylic acids or anhydrides thereof, such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride; and tri- or higher functional aliphatic carboxylic acids, such as 1,2,3,4-butanetetracarboxylic acid.

[0063] The polyester resin may be a synthetic resin or a commercially available product, such as MD1335, MD1480, and other Vylonal series resins (manufactured by Toyobo Co., Ltd.), and KT-0507, KT-8904, KT-8701, KT-9204, and other Elitel series resins (manufactured by Unitika Ltd.).

[0064] Of the 100% by mass of resin contained in the adhesive ink, the total content of the acrylic resin and polyester resin is 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. Furthermore, from the viewpoint of suppressing yellowing of the adhesive ink layer, the content of the acrylic resin in 100% by mass of the resin contained in the adhesive ink is preferably 65% ​​by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass.

[0065] In the present invention, when the resin is contained in the adhesive ink, it is preferably added as an emulsion, that is, the resin is preferably contained as emulsion particles in the adhesive ink of the present invention.

[0066] The preferred aspects of the composition and physical properties of the resin constituting the emulsion particles are the same as those described above.

[0067] The shape of the emulsion particles is not particularly limited, but they are usually spherical. The shape can be measured using a transmission electron microscope or a scanning electron microscope. The emulsion particles may have a single-layer structure or a multi-layer structure (e.g., a core-shell structure).

[0068] The average particle size (volume basis) of the emulsion particles is preferably 50 nm or more, more preferably 80 nm or more, even more preferably 100 nm or more, and is preferably 500 nm or less, more preferably 350 nm or less, even more preferably 300 nm or less. That is, the average particle size (volume basis) of the emulsion particles is preferably 50 to 500 nm, more preferably 80 to 350 nm, even more preferably 100 to 300 nm. By adjusting the average particle size of the emulsion particles within the above range, it becomes easier to incorporate emulsion particles at a high concentration while maintaining the viscosity of the adhesive ink within an appropriate range. The average particle size of the emulsion particles may be determined by the cumulant average particle size measured by dynamic light scattering, as shown in the examples below.

[0069] The resin (preferably emulsion particles) content in the adhesive ink of the present invention is, for example, 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and for example, 35% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less. That is, the resin (preferably emulsion particles) content in the adhesive ink of the present invention is, for example, 10 to 35% by mass, preferably 15 to 30% by mass, more preferably 20 to 25% by mass. By adjusting the resin content within the above range, the viscosity of the adhesive ink can be maintained within an appropriate range, while further enhancing the effects of the present invention.

[0070] <Solvent> The adhesive ink of the present invention contains water and a water-soluble organic solvent. These solvents act as diluents to adjust the viscosity of the adhesive ink. The total content of water and the water-soluble organic solvent in the adhesive ink can be set according to the desired viscosity of the adhesive ink and is not particularly limited, but is, for example, 40 to 90% by mass, preferably 50 to 88% by mass, and more preferably 55 to 85% by mass.

[0071] Examples of the water-soluble organic solvent include the same solvents as those described above as the water-soluble organic solvent used in emulsion polymerization. By including a water-soluble organic solvent in the adhesive ink, it is possible to improve moisture retention and compatibility with the resin. The water-soluble organic solvent may be used alone or in combination of two or more. The content of the water-soluble organic solvent is preferably 10 to 55 parts by mass, more preferably 15 to 45 parts by mass, per 100 parts by mass of water contained in the adhesive ink.

[0072] In particular, from the viewpoint of further enhancing moisture retention, water-soluble organic solvents having a boiling point of 150°C or higher are preferred, water-soluble organic solvents having a boiling point of 180°C or higher are more preferred, and water-soluble organic solvents having a boiling point of 200°C or higher are even more preferred. Examples of water-soluble organic solvents having a boiling point of 150°C or higher include propylene glycol, diethylene glycol, triethylene glycol, and glycerin. The content of the water-soluble organic solvent, which enhances moisture retention, is preferably 10 to 50 parts by mass, and more preferably 15 to 40 parts by mass, per 100 parts by mass of water contained in the adhesive ink. To enhance compatibility with the resin, a water-soluble organic solvent having a hydrophobic group (e.g., an alkyl group) and a hydroxyl group is preferred, with at least one selected from the group consisting of monoalkyl ethers of diethylene glycol, monoalkyl ethers of dipropylene glycol, monoalkyl ethers of polyethylene glycol (EO addition moles = 2 to 10), and monoalkyl ethers of polypropylene glycol (PO addition moles = 2 to 10). Among these, at least one selected from the group consisting of diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, monobutyl ethers of polyethylene glycol (EO addition moles = 2 to 4) (particularly triethylene glycol monobutyl ether), and monomethyl ethers of polypropylene glycol (PO addition moles = 2 to 10, preferably 2 to 4) (particularly tripropylene glycol monomethyl ether) is even more preferred. The content of the water-soluble organic solvent, which enhances compatibility, is preferably 1 to 15 parts by mass, more preferably 2 to 8 parts by mass, per 100 parts by mass of water contained in the adhesive ink.

[0073] The total content of the resin, water, and water-soluble organic solvent in the adhesive ink of the present invention is not particularly limited, but is, for example, 70% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, and may also be 100% by mass or 99.5% by mass or less.

[0074] <Crosslinking agent> The adhesive ink of the present invention may further contain a crosslinking agent. The use of a crosslinking agent is thought to result in the formation of a crosslinked structure through interaction with components contained in the adhesive ink of the present invention, such as a resin, or through a chemical reaction, thereby forming a tough coating film, which is believed to further improve the wet rub fastness and washing fastness (hereinafter sometimes collectively referred to as fastness) of the resulting printed textile.

[0075] Examples of the crosslinking agent include an isocyanate compound, an epoxy compound, a melamine compound, a metal chelate compound, an aziridine compound, a mercapto compound, and an oxazoline compound, and preferably an oxazoline compound. The crosslinking agent may be used alone or in combination of two or more.

[0076] The oxazoline compound as the crosslinking agent means a compound having two or more oxazoline groups in the molecule. Examples of the oxazoline 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, etc., but are not limited to these examples.

[0077] Among the above oxazoline compounds, water-soluble oxazoline compounds are preferred from the viewpoint of excellent crosslinking performance, and oxazoline group-containing polymers are also preferred. The above oxazoline group-containing polymers can be produced by conventionally known production methods. For example, a method of polymerizing a monomer component containing one or more addition-polymerizable oxazolines, or an addition-polymerizable oxazoline and a monomer copolymerizable with the addition-polymerizable oxazoline, is exemplified. The copolymerizable monomer is preferably a monomer copolymerizable with the addition-polymerizable oxazoline but lacking a functional group reactive with the oxazoline group. Examples of the above monomer components include monomers lacking a functional group reactive with the oxazoline group. Examples include (meth)acrylic monomers such as alkyl (meth)acrylates; styrene-based monomers such as styrene, α-methylstyrene, and chloromethylstyrene; vinyl-based monomers such as vinyl acetate, vinyl chloride, and vinyl benzoate; acrylonitrile; (meth)acrylamide-based monomers such as acrylamide; and olefin-based monomers such as ethylene and propylene.

[0078] 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.

[0079] Among the oxazoline group-containing polymers, water-soluble oxazoline group-containing polymers are preferred, and can be produced by the same method as the above-mentioned method for producing the oxazoline group-containing polymer. Examples of the water-soluble oxazoline group-containing polymer include polymers having an acrylic resin or the like as a main chain and containing oxazoline groups in side chains.

[0080] Commercially available oxazoline group-containing polymers can also be used. Examples include water-soluble polymers such as Epocross WS-500 and Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., and emulsion polymers such as Epocross K-2010, Epocross K-2020, and Epocross K-2030. Among these, water-soluble polymers such as Epocross WS-500 and Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., are preferred.

[0081] The content of the crosslinking agent (preferably, an oxazoline compound) is not particularly limited, but is, for example, 0 to 10 parts by mass, preferably 0.05 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and even more preferably 0.2 to 5 parts by mass, relative to 100 parts by mass of the resin.

[0082] <Surfactant> The adhesive ink of the present invention may further contain a surfactant, which makes it possible to adjust the surface tension to a level suitable for inkjet ejection.

[0083] As the surfactant, for example, an acetylene glycol surfactant, a silicone surfactant, a fluorine surfactant, or the like is preferably used. As the acetylene glycol surfactant, commercially available products may be used, and specific examples include the Surfynol series (manufactured by Evonik), the Olfine series (manufactured by Nissin Chemical Industry Co., Ltd.), and the Acetylenol series (manufactured by Kawaken Fine Chemicals Co., Ltd.). As the silicone surfactant, a polyether-modified silicone surfactant is preferably used. As the silicone surfactant, commercially available products may be used, and specific examples include the Silface series (manufactured by Nissin Chemical Industry Co., Ltd.), the KF series (manufactured by Nissin Chemical Industry Co., Ltd.), BYK-345, 347, 348, 349, 3450, 3451, 3455, and 3480 (all manufactured by BYK). Examples of the fluorine-based surfactant include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups on the side chains, etc. Commercially available products may be used as the fluorine-based surfactant, and specific examples include the Surflon series (manufactured by AGC Seiko Chemical Co., Ltd.) and the Megafac F series (manufactured by DIC Corporation). These surfactants may be used alone or in combination of two or more.

[0084] The surfactant is preferably an acetylene glycol surfactant or a silicone surfactant, more preferably a silicone surfactant, and even more preferably a polyether-modified silicone surfactant.

[0085] The content of the surfactant (the total content when two or more surfactants are used) is not particularly limited, but from the viewpoint of ejection stability, it is preferably 0.1 to 4 mass %, more preferably 0.5 to 3 mass %, even more preferably 1 to 2.5 mass %, and particularly preferably 1 to 2 mass %, relative to 100 mass % of the adhesive ink of the present invention. The content may also be 0.01 to 2 mass %, or 0.1 to 1 mass %.

[0086] The use of two or more of the above surfactants is preferable in that it makes it easier to adjust the surface tension to a level suitable for inkjet ejection. When two or more surfactants are used, the content of each surfactant is preferably 0.05 to 2.5% by mass, more preferably 0.2 to 2.0% by mass, and even more preferably 0.4 to 1.5% by mass, relative to 100% by mass of the adhesive ink of the present invention.

[0087] In particular, it is preferable to use a silicone surfactant in combination with an acetylene glycol surfactant, and it is more preferable to use a polyether-modified silicone surfactant in combination with an acetylene glycol surfactant, as this combination improves the ejection stability of the adhesive ink.

[0088] When a silicone surfactant and an acetylene glycol surfactant are used in combination, the mass ratio thereof (silicone surfactant / acetylene glycol surfactant) is preferably 0.1 to 20, more preferably 0.2 to 10, even more preferably 0.5 to 4.5, particularly preferably 0.7 to 3.0, and most preferably 1.0 to 2.0. In particular, it is preferable to adjust the mass ratio of the polyether-modified silicone surfactant to the acetylene glycol surfactant (polyether-modified silicone surfactant / acetylene glycol surfactant) to be within the above range.

[0089] <Colorant> The adhesive ink of the present invention may further contain a coloring material such as a dye or pigment. The presence of a coloring material in the adhesive ink allows the adhesive ink to also function as a colored ink, as described below. Specifically, it is possible to form a desired pattern such as an image or character using only the adhesive ink, or to form a white background layer that serves as the background for a pattern formed from a colored ink layer. This allows for a reduction in the number of times colored inks are printed, or the colored ink printing process itself to be omitted. From the viewpoint of achieving particularly excellent fastness of the resulting printed textile, it is preferable that the adhesive ink of the present invention does not contain a coloring material.

[0090] The coloring material is preferably a pigment from the viewpoint of fastness. Examples of the pigment contained in the adhesive ink include those exemplified as the pigment contained in the color ink described below, and preferred embodiments thereof are also the same.

[0091] The pigment content is, for example, 0 to 15% by mass or more, based on 100% by mass of the adhesive ink of the present invention. In particular, from the viewpoint of improving color development and design properties after transfer, the content is preferably 1% by mass or more, more preferably 1.5% by mass or more, and may be 2% by mass or more. Furthermore, from the viewpoint of improving hot-melt properties and fastness, the content is preferably 10% by mass or less, more preferably 7% by mass or less, and may be 5% by mass or less or 3% by mass or less. That is, the pigment content is preferably 1 to 10% by mass, more preferably 1.5 to 7% by mass, and may be 2 to 5% by mass or 2 to 3% by mass, based on 100% by mass of the adhesive ink of the present invention. When the pigment is a white pigment, the content of the white pigment is preferably 1 to 10 mass %, more preferably 1.5 to 7 mass %, relative to 100 mass % of the adhesive ink of the present invention, from the viewpoint of achieving both color development and design properties, as well as hot melt properties and fastness. Furthermore, when the pigment is a color pigment, the content of the color pigment is preferably 1 to 5 mass %, more preferably 1.5 to 3 mass %, relative to 100 mass % of the adhesive ink of the present invention, from the viewpoint of achieving both color development and design properties, hot melt properties, and fastness.

[0092] <Other ingredients> The adhesive ink of the present invention may contain other components in addition to the components described above, provided that the object of the present invention is not impaired. For example, the adhesive ink may contain appropriate amounts of additives such as dispersants, leveling agents, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, antifoaming agents, antioxidants, crosslinking accelerators, pH adjusters, preservatives, chain transfer agents, and chelating agents.

[0093] When the other components are added, their content is not particularly limited, but is preferably 2% by mass or less, more preferably 1% by mass or less, relative to 100% by mass of the adhesive ink of the present invention. In order to exert the effect of addition, their content is preferably 0.01% by mass or more, more preferably 0.05% by mass or more.

[0094] <Method of manufacturing adhesive ink> The method for producing the adhesive ink of the present invention is not particularly limited, but the adhesive ink can be produced, for example, by mixing a resin (preferably an emulsion as described below), water, a water-soluble organic solvent, and, if necessary, a crosslinking agent, a surfactant, a colorant, and other components.

[0095] As described above, in the adhesive ink of the present invention, the resin is preferably added in the form of an emulsion.

[0096] From the viewpoint of ease of handling, the content of emulsion particles in the emulsion is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 25 to 65% by mass. The content of emulsion particles can be determined as the non-volatile content (solid content) of the emulsion, and it is preferable to adjust the solid content of the emulsion to fall within the above range. In this specification, the non-volatile content (solid content) refers to the components excluding the solvent.

[0097] The solvent serving as the dispersion medium for the emulsion particles is preferably water or a mixed solvent of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include the same water-soluble organic solvents as those described above. The solvent serving as the dispersion medium for the emulsion particles may be derived from, for example, the solvent used in producing the resin, or may be derived from a solvent added separately to the produced resin or a commercially available resin. Alternatively, a commercially available emulsion may be used.

[0098] When mixing a resin (preferably an emulsion), water, a water-soluble organic solvent, and optionally a crosslinking agent, a surfactant, a coloring material, and other components, the crosslinking agent, surfactant, coloring material, and other additives may be used as they are, or may be added as a solution diluted or dispersed in a solvent or the like. In particular, when a pigment is used as the colorant, it is preferable to prepare a pigment dispersion in advance by mixing the pigment, dispersant, and solvent and dispersing the mixture using a bead mill or the like, thereby dispersing the pigment in the solvent, and then mix this with the other components. Examples of pigment dispersions used in the production of adhesive inks include those similar to the pigment dispersions used in the production of colored inks described below, and preferred embodiments thereof are also similar.

[0099] The method and order of mixing the above components are not particularly limited. After mixing, centrifugation, filtration, etc. may be carried out as needed.

[0100] As described above, the adhesive ink of the present invention is an inkjet adhesive ink used for transfer printing onto fabrics. That is, the present invention also encompasses a method of using the adhesive ink of the present invention as an adhesive ink for producing a transfer medium for use in transfer printing onto fabrics by an inkjet method. The adhesive ink used in the method is as described above, and the preferred embodiments thereof are also the same. Further, preferred embodiments of the transfer medium will be described in the section on transfer medium below.

[0101] 2. Ink set The present invention also encompasses an ink set containing the above-described adhesive ink and a colored ink containing a pigment and a resin.

[0102] The adhesive inks constituting the ink set of the present invention are as described above, and the preferred embodiments are also the same.

[0103] The hue of the colored inks constituting the ink set of the present invention is not particularly limited and may be selected from black, white, and chromatic colors. Chromatic colors include the three primary colors of subtractive color mixing, magenta, yellow, and cyan, as well as colors of different shades, such as light cyan, dark yellow, light magenta, and light black. Furthermore, the colored inks may be one or more hues selected from red, blue, orange, green, and violet. In this specification, a pigment that exhibits a white hue may be referred to as a white pigment, and a pigment that exhibits a hue other than white (chromatic colors or black) may be referred to as a colored pigment.

[0104] The hue of the color ink can be controlled by the pigment. The pigment contained in the color ink is not particularly limited, but pigments used in ordinary color inks for inkjet textile printing can be used. Examples of the pigment include organic pigments and inorganic pigments, which can be used alone or in combination of two or more types. If necessary, they can also be used in combination with an extender pigment.

[0105] Examples of organic pigments include azo pigments such as benzidine and Hansa Yellow, diazo pigments, azomethine pigments, methine pigments, anthraquinone pigments, phthalocyanine pigments such as phthalocyanine blue, perinone pigments, perylene pigments, diketopyrrolopyrrole pigments, thioindigo pigments, iminoisoindoline pigments, isoindolinone pigments such as iminoisoindolinone, dioxazine pigments, quinacridone pigments such as quinacridone red and quinacridone violet, flavanthrone pigments, indanthrone pigments, anthrapyrimidine pigments, carbazole pigments, monoarylide yellow, diarylide yellow, benzimidazolone yellow, tolyl orange, naphthol orange, and quinophthalone pigments.

[0106] The hue of the organic pigment is not particularly limited, and any pigment exhibiting the above-mentioned chromatic hue can be used. Specific examples of such organic pigments include CI Pigment Yellow, CI Pigment Red, CI Pigment Orange, CI Pigment Violet, CI Pigment Blue, and CI Pigment Green.

[0107] Examples of inorganic pigments include titanium dioxide, antimony trioxide, zinc oxides such as zinc white, lithopone, white lead, red iron oxide, black iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, ferric ferrocyanide (Prussian blue), ultramarine, and lead chromate. Other examples of inorganic pigments include flat-shaped pigments such as mica, clay, aluminum powder, talc, and aluminum silicate, as well as extender pigments such as calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, and magnesium carbonate. Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black.

[0108] Among inorganic pigments, preferred white pigments are titanium dioxide, antimony trioxide, zinc oxide such as zinc white, lithopone, white lead, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, magnesium carbonate, clay, talc, and aluminum silicate. Of these, titanium dioxide is preferred from the viewpoint of its high refractive index and excellent hiding power. Of titanium dioxide, titanium dioxide having a rutile crystal structure is preferred.

[0109] As the color pigment, the above-mentioned organic pigments, red iron oxide, black iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, ferric ferrocyanide (Prussian blue), ultramarine, lead chromate, etc. are preferred.

[0110] The average particle size (volume basis) of the pigment is preferably from 10 to 1000 nm, more preferably from 20 to 500 nm, from the viewpoint of dispersion stability, color development, or hiding power. In the case of a white pigment, the average particle diameter (volume basis) is preferably 100 to 500 nm from the viewpoint of superior hiding power, the lower limit is more preferably 150 nm or more, and even more preferably 200 nm or more, and the upper limit is more preferably 450 nm or less, and even more preferably 400 nm or less. In the case of color pigments, the average particle size (volume basis) is preferably 20 to 200 nm, particularly from the viewpoint of color development, with the lower limit being more preferably 40 nm or more, and even more preferably 50 nm or more, and the upper limit being more preferably 150 nm or less, and even more preferably 100 nm or less.

[0111] The average particle size (volume basis) of the pigment can be measured using a laser diffraction / scattering particle size distribution analyzer or dynamic light scattering. For example, the cumulant average particle size measured by dynamic light scattering, as shown in the examples below, can be used. However, in cases where measurement by dynamic light scattering is difficult, such as with black pigments, the 50% particle size in the volume-based particle size distribution measured using a laser diffraction / scattering particle size distribution analyzer can be used as the average particle size.

[0112] It is preferable that the pigment is dispersed and stabilized in the color ink with a dispersant. For this reason, in the production of the color ink, it is preferable to mix the pigment, dispersant, and solvent, and perform a dispersion treatment using a bead mill or the like to prepare a pigment dispersion in which the pigment is dispersed in the solvent, and then mix this with a resin and any optional components described below to produce the color ink.

[0113] Examples of the dispersant include poly(meth)acrylic acid (salts) such as poly(meth)acrylic acid and poly(meth)acrylate salts; copolymers of (meth)acrylic acid (salts) with one or more of the above-mentioned monomer components other than (meth)acrylic acid (salts), such as (meth)acrylic acid alkyl esters, (meth)acrylamide, styrene, maleic acid, maleic anhydride, maleic acid esters, and vinyl acetate; polyvinyl alcohol; and polyvinylpyrrolidone.

[0114] The solvent in the pigment dispersion is preferably an aqueous solvent, and examples of the aqueous solvent include the solvents described above as the aqueous solvent used in emulsion polymerization.

[0115] The content of the pigment in the color ink is preferably 1 to 50% by mass, and more preferably 2 to 35% by mass. In particular, when the pigment is a white pigment, the content of the white pigment in the color ink is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and when the pigment is an organic pigment, the content of the organic pigment in the color ink is preferably 1 to 30% by mass, more preferably 2 to 15% by mass.

[0116] There are no particular limitations on the type of resin contained in the colored inks that make up the ink set of the present invention, and examples include vinyl resins, acrylic resins, polyester resins, olefin resins, urethane resins, fluorine-based resins, silicone resins, epoxy resins, phenoxy resins, phenol resins, and xylene resins. Of these, acrylic resins and / or polyester resins are preferred, and acrylic resins are particularly preferred.

[0117] In particular, in the ink set of the present invention, it is preferable that the resin used in the color inks is a resin of the same type as the resin used in the adhesive ink. That is, in the ink set of the present invention, when an acrylic resin and / or a polyester resin is used as the adhesive ink, it is preferable that an acrylic resin and / or a polyester resin is also used as the resin used in the color inks. When an acrylic resin is used as the adhesive ink, it is more preferable that an acrylic resin is also used as the resin used in the color inks, or when a polyester resin is used as the adhesive ink, it is more preferable that a polyester resin is also used as the resin used in the color inks. By using this ink set, peeling is less likely to occur at the interface between the layer formed from the adhesive ink and the layer formed from the color ink on the transfer medium or the printed textile, resulting in further improvements in transferability and the fastness of the resulting printed textile.

[0118] The acrylic resin used in the colored ink may be a conventionally known acrylic resin. Among these, a resin containing a structural unit derived from a (meth)acrylic monomer is preferred. Specific examples of the (meth)acrylic monomer are the same as those described for the (meth)acrylic monomer used in the adhesive ink. The (meth)acrylic monomer preferably contains at least one selected from the group consisting of alkyl (meth)acrylate, (meth)acrylic acid (salt), and hydroxyalkyl (meth)acrylate, and more preferably contains all of (meth)acrylic acid (salt), alkyl (meth)acrylate, and hydroxyalkyl (meth)acrylate.

[0119] The alkyl (meth)acrylate may be selected from C 1-18 Alkyl (meth)acrylate is preferred, C 4-12 Alkyl (meth)acrylate is more preferred. In particular, the alkyl (meth)acrylate is at least C 4-12 It is preferable that the compound contains a chain alkyl acrylate, and C 4-12 Chain alkyl acrylate and C 4-12 It is more preferable that the cyclic alkyl methacrylate is contained.

[0120] The content of structural units derived from (meth)acrylic monomers (preferably the total content of structural units derived from (meth)acrylic acid (salt), alkyl (meth)acrylate, and hydroxyalkyl (meth)acrylate) relative to the total of 100% by mass of structural units derived from all monomer components constituting the acrylic resin used in the colored ink is preferably 30 to 100% by mass, more preferably 40 to 99% by mass, and even more preferably 55 to 95% by mass. The content of structural units derived from alkyl (meth)acrylate relative to the total of structural units derived from all monomer components constituting the acrylic resin used in the colored ink (100% by mass) is preferably 20 to 99% by mass, more preferably 30 to 98% by mass, and even more preferably 40 to 95% by mass. Also, C 4-12C relative to 100 parts by mass of structural units derived from chain alkyl acrylate 4-12 The content of the structural unit derived from a cyclic alkyl methacrylate is preferably from 1 to 100 parts by mass, more preferably from 3 to 50 parts by mass, and even more preferably from 5 to 20 parts by mass. The content of structural units derived from (meth)acrylic acid (salts) relative to the total of structural units derived from all monomer components constituting the acrylic resin used in the colored ink (100% by mass) is preferably 0.1 to 5% by mass, more preferably 0.5 to 4% by mass, and even more preferably 1.0 to 3% by mass. By adjusting the content within the above range, the rub fastness and wash fastness of the resulting printed textile can be further improved. The content of structural units derived from hydroxyalkyl (meth)acrylate relative to the total of structural units derived from all monomer components constituting the acrylic resin used in the colored ink (100% by mass) is preferably 0.1 to 5% by mass, more preferably 0.3 to 4% by mass, and even more preferably 0.5 to 3% by mass. By adjusting the content within the above range, the water resistance of the resulting printed textile can be improved.

[0121] The acrylic resin used in the colored ink may further contain a structural unit derived from a styrene-based monomer. The total content of the structural units derived from (meth)acrylic monomers and the structural units derived from styrene-based monomers is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 95% by mass or more, relative to 100% by mass of the total structural units derived from all monomer components constituting the acrylic resin used in the colored ink. Specific examples of the styrene-based monomer are the same as those described for the styrene-based monomer used in the adhesive ink. The content of the structural units derived from styrene-based monomers relative to 100 parts by mass of the structural units derived from (meth)acrylic monomers is, for example, 10 to 150 parts by mass, preferably 30 to 100 parts by mass, and more preferably 40 to 70 parts by mass.

[0122] The acrylic resin used in the colored ink may further contain structural units derived from monomers other than (meth)acrylic monomers and styrene monomers. Examples of monomers other than (meth)acrylic monomers and styrene monomers include the acid group-containing monomers (excluding (meth)acrylic acid) used in the adhesive ink and the monomers described as other monomers.

[0123] The polyester resin used in the color ink may be a conventionally known polyester resin, preferably a condensation polymer of an aromatic dicarboxylic acid and a diol compound, and specific examples of the aromatic dicarboxylic acid and the diol compound are the same as those described above.

[0124] The weight-average molecular weight (Mw) of the resin used in the color ink is not particularly limited, but from the viewpoint of suppressing flow of the color ink after printing, it is preferably 50,000 or more, more preferably 300,000 or more, even more preferably 550,000 or more, and particularly preferably 600,000 or more. The upper limit of the weight-average molecular weight of the resin used in the color ink is preferably 5,000,000 or less, from the viewpoint of improving film-forming properties and water resistance.

[0125] The glass transition temperature (Tg (°C)) of the resin used in the color ink is not particularly limited, but from the viewpoint of further improving the texture of the resulting printed textile, it is preferably −50 to 10°C, more preferably −45 to 5°C, and even more preferably −40 to 3°C.

[0126] When a resin is added to a color ink, it is preferably added as an emulsion, i.e., the resin is preferably contained in the color ink as emulsion particles. The preferred aspects of the composition and physical properties of the resin constituting the emulsion particles are the same as those described above.

[0127] The content of the resin (preferably emulsion particles) in the color ink is, for example, 5 to 40% by mass, preferably 8 to 30% by mass, and more preferably 10 to 25% by mass. By adjusting the content of the resin within the above range, the viscosity of the color ink can be maintained within an appropriate range.

[0128] The color ink preferably further contains a solvent. While organic solvents and aqueous solvents can be suitably used as the solvent, it is preferable to use an aqueous solvent from the viewpoint of reducing the environmental impact. Examples of aqueous solvents include water and mixed solvents of water and a water-soluble organic solvent. From the viewpoint of improving moisture retention and compatibility with resins, the aqueous solvent contained in the color ink preferably contains a water-soluble organic solvent. The preferred aspects of the type and content of the water-soluble organic solvent are the same as the preferred aspects of the type and content of the water-soluble organic solvent in the adhesive ink.

[0129] The content of the solvent in the color ink can be set according to the desired viscosity of the color ink and is not particularly limited, but is, for example, 40 to 90% by mass, preferably 50 to 88% by mass, and more preferably 55 to 85% by mass.

[0130] The color ink may further contain a crosslinking agent. The use of a crosslinking agent is thought to further improve the wet rub fastness and washing fastness of the resulting printed textile, possibly because a crosslinked structure is formed through an interaction with a component contained in the color ink, such as a resin, or through a chemical reaction, and a tough coating film is formed. Examples of crosslinking agents that can be used in the color ink include the compounds exemplified as crosslinking agents that can be used in the adhesive ink, and preferred embodiments thereof are also the same.

[0131] The content of the crosslinking agent is not particularly limited, but is, for example, 0 to 10 parts by mass, preferably 0.05 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and even more preferably 0.2 to 5 parts by mass, relative to 100 parts by mass of the resin.

[0132] The color ink may further contain a surfactant. Examples of surfactants that can be used in the color ink include the compounds exemplified as surfactants that can be used in the adhesive ink, and preferred embodiments thereof are also the same.

[0133] The content of the surfactant is not particularly limited, but is preferably 0.01 to 2% by mass, and more preferably 0.1 to 1% by mass, relative to 100% by mass of the color ink.

[0134] The color ink may contain other components in addition to the components described above, provided that the object of the present invention is not impaired. For example, the color ink may contain appropriate amounts of additives such as leveling agents, UV absorbers, UV stabilizers, thickeners, humectants, plasticizers, stabilizers, defoamers, dyes, antioxidants, crosslinking accelerators, pH adjusters, and preservatives. When the above-mentioned other components are added, their content is not particularly limited, but is preferably 2% by mass or less, and more preferably 1% by mass or less, relative to 100% by mass of the color ink. Furthermore, to achieve the desired effect, the content is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more.

[0135] 3. Transfer medium The present invention also encompasses transfer media in which the adhesive ink of the present invention is printed on a transfer substrate, with or without a colored ink layer formed from a colored ink containing a pigment and a resin. The transfer medium of the present invention is formed using the adhesive ink described above, and therefore, use of this transfer medium provides excellent transferability during transfer printing onto fabrics, and can improve the wet rub fastness and texture of the resulting printed textile. Note that the transfer medium in which the adhesive ink is printed on the transfer substrate via a colored ink layer is preferably a transfer medium in which a colored ink containing a pigment and a resin is printed on the transfer substrate, and the adhesive ink of the present invention is further printed on the colored ink. Hereinafter, a layer formed by printing colored ink, i.e., a layer formed from colored ink, may be referred to as a colored ink layer, and a layer formed by printing adhesive ink, i.e., a layer formed from adhesive ink, may be referred to as an adhesive ink layer. The color ink layer and adhesive ink layer in the transfer medium of the present invention are formed so as to be releasable from the transfer substrate.

[0136] When the transfer medium of the present invention is a transfer medium in which an adhesive ink is printed on a transfer substrate via a colored ink layer, the transfer medium can be said to be laminate A in which a colored ink layer is provided on the transfer substrate and an adhesive ink layer is further provided on the colored ink layer. When the transfer medium of the present invention is a transfer medium in which an adhesive ink is printed on a transfer substrate without a colored ink layer, the transfer medium can be said to be laminate B in which an adhesive ink layer is laminated on a transfer substrate. In particular, when the adhesive ink that forms the adhesive ink layer contains a colorant, it is preferable to use the transfer medium in the form of laminate B. Furthermore, the transfer medium of the present invention can be said to be a laminate in which the adhesive ink layer in the laminates A and B is an adhesive ink layer containing a resin (the resin contained in the adhesive ink described above) having a glass transition temperature of 30°C or less and a weight average molecular weight of 10,000 to 700,000.

[0137] Hereinafter, a transfer medium (i.e., laminate A) on which the adhesive ink of the present invention is printed via a colored ink layer on a transfer substrate may be referred to as transfer medium A, and a transfer medium (i.e., laminate B) on which the adhesive ink of the present invention is printed without a colored ink layer may be referred to as transfer medium B.

[0138] FIG. 1 is a schematic cross-sectional view showing an example of the layered structure of the transfer medium of the present invention. 1(a) and (b) are examples of transfer medium A. The transfer medium 100 in (a) and (b) has a colored ink layer 2 provided on a transfer substrate 1, and an adhesive ink layer 3 provided on the colored ink layer 2. The adhesive ink layer 3 may be provided only in the area where the colored ink layer 2 is formed, as shown in FIG. 1(a), or may be provided in the area where the colored ink layer 2 is formed as well as around it, as shown in FIG. 1(b). The embodiment shown in (b) is preferred because it further improves the wet rub fastness of the resulting printed textile. 1(c) is an example of transfer medium B. In the transfer medium 100 in (c), the adhesive ink layer 3 is laminated directly on the transfer substrate 1. In particular, when the adhesive ink forming the adhesive ink layer 3 contains a colorant, it is preferable to use the form of transfer medium B (for example, the form shown in FIG. 1(c)).

[0139] The transfer substrate is not particularly limited, but is preferably a material that does not shrink easily during the drying process described below. Specific examples of the transfer substrate include metal, wood, plastic, and paper. Examples of the metal include aluminum and copper, with aluminum being preferred from the viewpoint of cost. Examples of the plastic include polyolefin resin, polyester resin, polyamide resin, and polycarbonate resin. From the viewpoint of cost, polyester resin is preferred, and aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate are more preferred. Examples of the paper include plain paper, fine paper, and coated paper.

[0140] In particular, the transfer substrate is preferably plastic or paper from the viewpoint of cost, and more preferably polyester resin from the viewpoint of good heat resistance, more preferably aromatic polyester, and particularly preferably polyethylene terephthalate.

[0141] The transfer substrate may have a single layer structure or a multilayer structure.

[0142] The transfer substrate is preferably in the form of a sheet or film to facilitate use of the transfer medium, and the thickness of the transfer substrate is preferably 10 to 50 μm.

[0143] The transfer medium of the present invention preferably has an ink-receiving layer provided on the surface of the transfer substrate on which the colored ink and / or adhesive ink is printed. Specifically, transfer medium A preferably has an ink-receiving layer between the transfer substrate and the colored ink layer, and transfer medium B preferably has an ink-receiving layer between the transfer substrate and the adhesive ink layer. The provision of the ink-receiving layer can prevent the colored ink or adhesive ink printed on the ink-receiving layer from flowing or crumbling, and can further increase the durability of the colored ink layer or adhesive ink layer after transfer to the fabric.

[0144] 2 is a schematic cross-sectional view showing an example of the layer structure of a transfer medium A having an ink-receiving layer. The transfer medium 100 has an ink-receiving layer 4 on a transfer substrate 1, a colored ink layer 2 on the ink-receiving layer 4, and an adhesive ink layer 3 on the colored ink layer 2. When the transfer medium B is used, the transfer medium 100 may be formed by providing an ink receiving layer 4 on a transfer substrate 1 and laminating an adhesive ink layer 3 on the ink receiving layer 4 .

[0145] The ink-receiving layer can be formed by coating a transfer substrate (or a transfer substrate provided with a release layer, as described below) with a solution containing a resin for forming the ink-receiving layer. Examples of such resins include (meth)acrylic resins such as (meth)acrylic ester resins and (meth)acrylic ester-styrene copolymer resins; olefin resins such as polyethylene resins and polypropylene resins; silicone resins; polyvinyl alcohol resins; and cellulose resins such as sodium carboxymethyl cellulose. The solution containing the resin for forming the ink-receiving layer may further contain inorganic particles such as calcium carbonate and silica.

[0146] The thickness of the ink-receiving layer is not particularly limited, but is preferably 30 nm or more, more preferably 100 nm or more, from the viewpoint of suppressing the flow of color inks and adhesive inks. From the viewpoint of cost, it is preferably 20 μm or less, more preferably 10 μm or less. That is, the thickness of the ink-receiving layer is preferably 30 nm to 20 μm, more preferably 100 nm to 10 μm.

[0147] The transfer medium of the present invention may also have a release layer on at least one surface of the transfer substrate. Specifically, transfer medium A may have a release layer between the transfer substrate and the colored ink layer (preferably the ink-receiving layer) and / or on the side of the transfer substrate opposite the side on which the colored ink layer is formed. Transfer medium B may have a release layer between the transfer substrate and the adhesive ink layer (preferably the ink-receiving layer) and / or on the side of the transfer substrate opposite the side on which the adhesive ink layer is formed. By providing a release layer between the transfer substrate and the colored ink layer or between the transfer substrate and the adhesive ink layer (preferably between the transfer substrate and the ink-receiving layer), the transfer medium can easily peel the colored ink layer or adhesive ink layer to be transferred from the transfer substrate, thereby facilitating transfer from the transfer medium to the fabric. Furthermore, by providing a release layer on the side of the transfer medium opposite the side on which the colored ink layer or adhesive ink layer is formed, blocking between the transfer media can be suppressed when the transfer media are stacked.

[0148] FIG. 3 is a schematic cross-sectional view showing an example of the layered structure of a transfer medium A having an ink-receiving layer and a release layer. The transfer medium 100 in FIG. 3(d) has a release layer 5 on a transfer substrate 1, an ink-receiving layer 4 on the release layer 5, a colored ink layer 2 on the ink-receiving layer 4, and an adhesive ink layer 3 on the colored ink layer 2. The transfer medium 100 in FIG. 3(e) has an ink-receiving layer 4 on one side of the transfer substrate 1 and a release layer 5 on the other side, a colored ink layer 2 on the ink-receiving layer 4, and an adhesive ink layer 3 on the colored ink layer 2. The transfer medium 100 in FIG. 3(f) has a release layer 5 on both sides of the transfer substrate 1, an ink-receiving layer 4 on one release layer 5, a colored ink layer 2 on the ink-receiving layer 4, and an adhesive ink layer 3 on the colored ink layer 2. When the transfer medium B is used, it is sufficient to use a transfer medium 100 in which the adhesive ink layer 3 is directly laminated on the ink receiving layer 4 in FIGS. 3(d) to 3(f).

[0149] The release layer is preferably a layer obtained by coating at least one surface of the transfer substrate with a release agent, such as a polyethylene wax-based release agent, a silicone-based release agent, or a fluorine-based release agent.

[0150] The thickness of the release layer is not particularly limited, but is preferably 10 nm or more, more preferably 30 nm or more, from the viewpoint of further improving transferability, and is preferably 2 μm or less from the viewpoint of reducing bulkiness when made into a roll-shaped transfer medium.

[0151] Sheets or films in which an ink-receiving layer and / or a release layer are provided on a transfer substrate are commercially available, and the transfer medium may be constructed using such commercially available products, such as DTF Transfers film (manufactured by One More Buck).

[0152] In the transfer medium of the present invention, the color inks that form the color ink layer are the same as those described above as the color inks that make up the ink set, and the preferred embodiments thereof are also the same.

[0153] The color ink layer may be a single layer or multiple layers. For example, by providing a color ink layer that forms the target image or characters (hereinafter sometimes referred to as a pattern) on the transfer substrate side and providing a color ink layer that exhibits a white hue on top of that (i.e., on the adhesive ink layer side), good color development can be achieved even when the fabric that is the transfer medium is a dark fabric such as black.

[0154] When the transfer medium has an ink-receiving layer, a part or all of the colored ink layer and / or adhesive ink layer laminated on the ink-receiving layer may be absorbed into the ink-receiving layer. In particular, when the transfer medium A has an ink-receiving layer, a part or all of the colored ink layer may be absorbed into the ink-receiving layer. Furthermore, when the transfer medium B has an ink-receiving layer, a part of the adhesive ink layer may be absorbed into the ink-receiving layer.

[0155] The ejection weight of the color ink per unit area in the transfer medium of the present invention is not particularly limited, but is preferably 1 to 200 g / m 2 is preferable, and 5 to 100 g / m 2 By forming a colored ink layer within this range, a printed product having even more excellent feel and wet rub fastness tends to be obtained.

[0156] In the transfer medium of the present invention, the adhesive ink that forms the adhesive ink layer is the same as that explained above as the adhesive ink, and the preferred embodiments thereof are also the same.

[0157] The thickness of the adhesive ink layer in the transfer medium of the present invention is not particularly limited, but is preferably 0.5 μm or more, more preferably 2 μm or more, even more preferably 5 μm or more or more than 5 μm, and particularly preferably 8 μm or more, in terms of film thickness after drying. By adjusting the adhesive ink to the above thickness, the transferability and wet rub fastness of the resulting printed textile are improved. Furthermore, from the viewpoint of improving the texture of the resulting printed textile, the thickness of the adhesive ink layer is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 100 μm or less, and may be 50 μm or less. That is, the thickness of the adhesive ink layer is preferably 0.5 to 200 μm, more preferably 2 to 150 μm, even more preferably 5 to 100 μm, particularly preferably 8 to 100 μm, and may be 8 to 50 μm.

[0158] <Method of manufacturing the transfer medium> The method for producing the transfer medium of the present invention is not particularly limited. Step 3: printing an adhesive ink by inkjet onto a transfer substrate or onto a colored ink layer laminated on the transfer substrate; and It is preferable to produce the adhesive ink by a method including a step 4 of drying the adhesive ink.

[0159] When the step 3 is a step of printing an adhesive ink by inkjet onto a colored ink layer laminated on a transfer substrate, the colored ink layer is preferably formed by step 1 of printing a colored ink by inkjet onto a transfer substrate, and step 2 of drying the colored ink. Each step will be described in detail below.

[0160] [Process 1] Step 1 is a step of printing colored inks onto a transfer substrate by inkjet printing. An example of an apparatus for performing Step 1 is an inkjet recording apparatus. A specific example of an inkjet recording apparatus is, but is not limited to, MMP-TX13 (manufactured by Mastermind). When using an inkjet recording apparatus, colored inks can be printed onto the transfer substrate by ejecting the colored inks from an inkjet head and depositing the colored inks onto predetermined areas of the transfer substrate. This forms a pattern of a colored ink layer on the transfer substrate. Note that "printing colored inks onto a transfer substrate by inkjet printing" not only refers to an embodiment in which colored inks are directly printed onto a transfer substrate by inkjet printing, but also includes an embodiment in which colored inks are printed onto a laminate having other layers, such as an ink-receiving layer and / or a release layer, on the transfer substrate by inkjet printing.

[0161] The color inks used in step 1 are the same as those described above as the color inks constituting the ink set, and the preferred embodiments thereof are also the same.

[0162] The number of times the color inks are printed is not particularly limited and is, for example, 1 to 6 times, preferably 1 to 4 times. When printing is performed multiple times, the color inks used in each printing may be the same or different. For example, after printing using color inks to form a pattern such as a desired image or text, printing may be performed using a white color ink. By performing such a printing process, a white background layer is formed between the fabric and the pattern in the resulting printed textile, which improves color development, particularly when using a dark-colored fabric. Note that when an adhesive ink containing a white pigment is used in step 3 described below to form a white background layer between the fabric and the pattern, the printing step of the white color ink can be omitted.

[0163] In step 1, the amount of ink ejected in one printing is not particularly limited and may be determined depending on the desired thickness of the color ink layer, and may be adjusted within the range of, for example, 3 to 15 ng.

[0164] [Process 2] Step 2 is a step of drying the color ink printed on the transfer substrate. That is, step 2 can be said to be a step of evaporating some or all of the components (i.e., solvent) excluding the solid content of the color ink printed on the transfer substrate. Even if an ink-receiving layer is provided on the printing surface of the transfer substrate, when an adhesive ink is printed on top of it, the color ink may flow and a clear pattern may not be obtained, so it is preferable to go through drying step 2.

[0165] In step 2, of 100% by mass of the components of the color ink excluding solids, preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more is evaporated. By adjusting the evaporation amount within the above range, it is possible to prevent the adhesive ink from flowing in step 3, which will be described later. Furthermore, in step 2, of 100% by mass of the components of the color ink excluding solids, preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or more, and particularly preferably 50% by mass or less or 40% by mass or less is evaporated. By adjusting the evaporation amount within the above range, the color ink layer and the adhesive ink layer are appropriately mixed at the interface between them, preventing peeling at the interface during transfer printing, thereby further improving transferability. That is, the evaporation amount is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, even more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass or 20 to 40% by mass. The conditions for achieving the desired evaporation amount can be determined by first ejecting a fixed weight of colored ink with a known solid content onto a substrate, measuring the total weight of the ink and substrate after drying, and the weight of the substrate alone using a precision balance, and then calculating the weight.The drying process in step 2 can be carried out under the same conditions.

[0166] The device for performing step 2 is not particularly limited, but for example, a heating means in an inkjet recording device (e.g., a platen heater, a hot air heater, an infrared heater) can be used. Among these, it is preferable to use a platen heater from the viewpoint of uniform drying. If the inkjet recording device does not have a platen heater, a planar heating element such as a rubber heater can be installed on the platen of the inkjet recording device as an alternative to the platen heater.

[0167] The evaporation rate can be adjusted by controlling the heating temperature, heating time, hot air temperature, and air volume. It is preferable to set the heater conditions by measuring the evaporation rate beforehand before an experiment. For example, when using a platen heater or an alternative planar heating element, the colored ink can be dried by heating the backside of the transfer substrate with the platen heater or planar heating element. From the viewpoint of shortening the heating time, the heating temperature of the platen heater or planar heating element is preferably 30°C or higher, more preferably 40°C or higher. Furthermore, if the heating temperature of the platen heater or planar heating element is too high, heat may be transferred to the inkjet head, causing nozzle clogging. Therefore, the heating temperature is preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 60°C or lower. That is, the heating temperature of the platen heater or planar heating element is preferably 30 to 80°C, more preferably 40 to 70°C, and even more preferably 40 to 60°C.

[0168] Step 2 may be performed simultaneously with step 1, after step 1, or simultaneously with and after step 1. When step 2 is performed simultaneously with step 1, step 2 may be performed continuously from the start to the end of step 1, or may be performed intermittently, but continuous drying is preferred. For example, when printing colored inks multiple times, it is preferable to dry the colored inks during and / or after printing each colored ink. In this case, the evaporation amount of components excluding solids in each colored ink may be adjusted to fall within the above range, or the evaporation amount of components excluding solids in all colored inks may be adjusted to fall within the above range.

[0169] A colored ink layer can be laminated on the transfer substrate through steps 1 and 2. The colored ink layer forms a pattern such as a desired image or character, but if the adhesive ink used in step 3 described below contains a colorant, the desired pattern can be formed by the adhesive ink, and steps 1 and 2 can be omitted.

[0170] [Process 3] Step 3 is a step of inkjet printing an adhesive ink onto the transfer substrate or onto a colored ink layer laminated on the transfer substrate. The above-mentioned "step of inkjet printing an adhesive ink onto a transfer substrate" includes not only an embodiment in which the adhesive ink is directly printed onto the transfer substrate by inkjet, but also an embodiment in which the adhesive ink is printed onto a laminate provided with other layers (excluding the colored ink layer) such as an ink-receiving layer and / or a release layer on the transfer substrate by inkjet. For example, when producing transfer medium A having an ink-receiving layer, it is preferable that the printing of the adhesive ink in step 3 is carried out on the surface of the colored ink layer side of a laminate in which the transfer substrate, the ink-receiving layer, and the colored ink layer are laminated in this order, and when producing transfer medium B having an ink-receiving layer, it is preferable that the printing of the adhesive ink in step 3 is carried out on the ink-receiving layer laminated on the transfer substrate.

[0171] The adhesive ink used in step 3 is the same as that described above as the adhesive ink, and the preferred embodiments thereof are also the same.

[0172] An example of an apparatus for performing step 3 is an inkjet recording apparatus similar to that used in step 1. When using an inkjet recording apparatus, the adhesive ink can be printed by ejecting the adhesive ink from an inkjet head and depositing the adhesive ink onto the transfer substrate, or onto the ink-receiving layer and / or release layer provided on the transfer substrate, or onto the colored ink layer formed in step 2. This results in an adhesive ink layer being formed on the transfer substrate, or onto the ink-receiving layer and / or release layer provided on the transfer substrate, or onto the colored ink layer. When printing (depositing) the adhesive ink onto the colored ink layer, printing (depositing) it not only onto the colored ink layer but also around it can produce a transfer medium such as that shown in Figure 1(b).

[0173] By using an inkjet recording device equipped with a plurality of inkjet heads, it is possible to perform printing of color inks and printing of adhesive inks consecutively. For example, by installing the above-mentioned ink set containing one or more types of color inks and adhesive ink in the ink cartridges for each color of the inkjet recording device and ejecting ink from each inkjet head corresponding to each ink cartridge, it is possible to perform printing of color inks and printing of adhesive ink consecutively.

[0174] The number of times the adhesive ink is printed is not particularly limited and may be determined depending on the desired thickness of the adhesive ink layer, but may be, for example, 1 to 6 times, and preferably 1 to 4 times. Furthermore, in step 3, the amount of ink ejected per printing is not particularly limited and may be determined depending on the desired thickness of the adhesive ink layer, but may be adjusted within the range of, for example, 3 to 15 ng.

[0175] [Step 4] Step 4 is a step of drying the adhesive ink printed on the transfer substrate or the color ink. That is, step 4 can be said to be a step of evaporating some or all of the components (i.e., solvent) excluding the solid content of the color ink or adhesive ink printed in step 1 or step 3.

[0176] In step 4, preferably 80 to 100 mass %, and more preferably 90 to 100 mass %, of 100 mass % of the components excluding the solid content in the adhesive ink, is evaporated.

[0177] The device for performing step 4 is not particularly limited, but examples include heating means in an inkjet recording device (e.g., a platen heater, a hot air heater, an infrared heater, etc.) and a planar heating element such as a rubber heater installed on the platen and used as an alternative to a platen heater. The evaporation rate can be adjusted by controlling the heating temperature, heating time, hot air temperature, and air volume. It is preferable to set the conditions for the heater by measuring the evaporation rate beforehand prior to the experiment. For example, when using a platen heater or an alternative planar heating element, the color ink and adhesive ink can be dried by heating the backside of the transfer substrate with the platen heater or planar heating element. The heating temperature of the platen heater or planar heating element is preferably 30°C or higher, more preferably 40°C or higher, from the viewpoint of shortening the heating time. Furthermore, if the heating temperature of the platen heater is too high, heat may be transferred to the inkjet head, potentially causing nozzle clogging. Therefore, the heating temperature is preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 60°C or lower. That is, the heating temperature of the platen heater or the planar heating element is preferably 30 to 80°C, more preferably 40 to 70°C, and even more preferably 40 to 60°C.

[0178] It is also preferable to dry the transfer medium after step 3 or after heating by the heating means of the inkjet recording apparatus or an alternative means thereof, using means such as natural drying, heating, reduced pressure, or contact with dry air or hot air. In these means, the heating temperature, heating time, pressure, hot air temperature, and air volume may be appropriately set depending on the desired evaporation amount. For example, when drying by heating or contact with hot air, the heating temperature and hot air temperature are preferably 40 to 180°C, more preferably 80 to 160°C, and even more preferably 100 to 150°C. The heating time and hot air contact time are preferably 0.5 to 30 minutes, more preferably 1 to 10 minutes.

[0179] Step 4 may be performed simultaneously with step 3, after step 3, or simultaneously with and after step 3. When step 4 is performed simultaneously with step 3, it may be performed continuously from the start to the end of step 3, or may be performed intermittently. In particular, it is preferable to perform drying using a heating means in an inkjet recording apparatus continuously during step 3, and then dry by heat or contact with hot air after step 3. Furthermore, when printing adhesive inks multiple times, it is preferable to dry the adhesive inks using a heating means in an inkjet recording apparatus or an alternative means during and / or after printing of each adhesive ink, and then dry by heat or contact with hot air after all printing is completed. In this case, the evaporation amount of components excluding solids in each adhesive ink may be adjusted to within the above range, or the evaporation amount of components excluding solids in all adhesive inks may be adjusted to within the above range.

[0180] 4. Textile printing The present invention also encompasses textile prints that have been transfer printed using the above-described adhesive ink, i.e., textile prints that have been transfer printed using the above-described transfer medium. Because the printed textile of the present invention uses a specific adhesive ink, it has excellent wet rub fastness and texture. The method for producing the printed textile of the present invention will be described in detail below.

[0181] <Method of manufacturing printed items> The printed textile of the present invention can be obtained by transfer printing the above-mentioned transfer medium onto a fabric. The transfer medium used in producing the printed textile of the present invention is the same as that described above as the transfer medium, and preferred embodiments thereof are also the same.

[0182] The fabric used is not particularly limited and includes all textile products such as cloth and textiles made from natural and / or synthetic fibers. Examples of the fabric include woven fabric, nonwoven fabric, knitted fabric, etc. The fibers constituting the fabric are also not particularly limited and include, for example, natural fibers, chemical fibers, and mixtures thereof.

[0183] 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 made from cotton, polyester fibers, polypropylene fibers, nylon fibers, or mixtures thereof are preferred.

[0184] The transfer printing method is not particularly limited, and any conventionally known method can be used. For example, transfer printing preferably includes a step of bringing the surface of a transfer medium on which an adhesive ink layer has been formed (i.e., the adhesive ink-printed surface) into close contact with a fabric while facing the fabric, and a step of peeling the transfer substrate from the fabric. This allows the transfer substrate to be peeled off while leaving the printed adhesive ink (adhesive ink layer) on the fabric side.

[0185] 4 is a schematic cross-sectional view showing an example of a laminated structure of transfer medium A and fabric in the contacting step. The transfer medium 100 is arranged so that the surface on which the adhesive ink layer 3 is formed faces the fabric 6, and they are in close contact with each other. It is preferable that a portion of the adhesive ink layer 3 is embedded in the fabric 6. This further improves the wet rub fastness of the resulting printed textile. The same applies when transfer medium B is used.

[0186] The above-mentioned contacting step preferably includes heating and pressurizing as necessary. For example, the contacting step may include a method in which the transfer medium is brought into close contact with the fabric using a press or a heated drum, and then heated and pressurized.

[0187] The heating temperature in the adhesion step is not particularly limited, but is preferably 80 to 200°C, and more preferably 100 to 180°C. The pressure in the adhesion process is not particularly limited, but is preferably 100 to 600 g / cm 2 is preferable, and more preferably 200 to 500 g / cm 2 is.

[0188] The contact time is preferably 1 second or more, more preferably 3 seconds or more, from the viewpoint of further improving transferability. The upper limit of the contact time is not particularly limited, but from the viewpoint of productivity, it is preferably 1 minute or less, more preferably 30 seconds or less. That is, the contact time is preferably 1 second to 1 minute, more preferably 3 seconds to 30 seconds.

[0189] After the adhesion step, the transfer substrate is peeled off from the fabric to obtain a printed item. From the viewpoint of reducing ink remaining on the transfer substrate, it is preferable to peel off the transfer substrate after the temperature of the fabric has reached 60°C or less (particularly 40°C or less).

[0190] The obtained printed textile may be further heated and pressed using a press or a heated drum, etc. By subjecting the obtained printed textile to additional heating and pressing treatment, the ink and the fabric are more firmly bonded to each other, and wet rubbing fastness is further improved. The heating temperature in this step is not particularly limited, but is preferably 80 to 200°C, and more preferably 100 to 180°C. The pressure in this step is not particularly limited, but is preferably 100 to 600 g / cm 2 is preferable, and more preferably 200 to 500 g / cm 2 is. The heating and pressurizing time in this step is not particularly limited, but is preferably 1 second to 1 minute, and more preferably 3 seconds to 30 seconds.

[0191] This application claims the benefit of priority based on Japanese Patent Application No. 2023-024440, filed February 20, 2023, and Japanese Patent Application No. 2023-027251, filed February 24, 2023. The entire contents of the specification of Japanese Patent Application No. 2023-024440, filed February 20, 2023, and the entire contents of the specification of Japanese Patent Application No. 2023-027251, filed February 24, 2023, are incorporated herein by reference. [Example]

[0192] 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."

[0193] [Ink Adjustment]

[0194] (Emulsion Production Example 1) A polymerization vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube, and dropping funnel was charged with 280 parts of deionized water. The internal temperature was then raised to 75°C while stirring under a nitrogen gas stream. Meanwhile, the dropping funnel was charged with a monomer emulsion consisting of 490 parts of methyl methacrylate, 490 parts of butyl acrylate, 20 parts of acrylic acid, 4.0 parts of t-dodecyl mercaptan as a polymerization chain transfer agent, 62.5 parts of Softanol 300 (manufactured by Nippon Shokubai Co., Ltd.) and 62.5 parts of Latemul WX (trade name, manufactured by Kao Corporation), each of which had been prepared as a 20% aqueous solution, and 183.0 parts of deionized water. Next, while maintaining the internal temperature of the polymerization vessel at 75°C, 27.0 parts of the above monomer emulsion and 5 parts of a 5% aqueous potassium persulfate solution and 10 parts of a 2% aqueous sodium bisulfite solution as polymerization initiators (oxidizers) were added to initiate prepolymerization. After 40 minutes, the remaining monomer emulsion was added dropwise over 210 minutes while maintaining the reaction system at 80°C. Simultaneously, 95 parts of a 5% aqueous potassium persulfate solution and 90 parts of a 2% aqueous sodium bisulfite solution were added dropwise over 210 minutes. After the completion of the addition, the temperature was maintained for 60 minutes to terminate the polymerization. The resulting reaction solution was cooled to room temperature, and then 16.7 parts of 2-dimethylethanolamine and 39 parts of deionized water were added to obtain an acrylic resin emulsion (hereinafter referred to as Emulsion 1). The solid content of emulsion 1 was 55%, and the emulsion particles contained in emulsion 1 had a Tg of 10° C., an average particle size of 200 nm, and a weight average molecular weight of 300,000.

[0195] (Emulsion Production Example 2) An acrylic resin emulsion (hereinafter referred to as emulsion 2) was obtained by carrying out a reaction in the same manner as in emulsion production example 1, except that 62.5 parts of LATEMULL WX prepared into a 20% aqueous solution was used instead of 62.5 parts of ADEKA REASORB SR-10 (trade name, manufactured by ADEKA Corporation) prepared into a 20% aqueous solution. The solids content of emulsion 2 was 55%, and the Tg of the emulsion particles contained in emulsion 2 was 8°C, the average particle size was 200 nm, and the weight average molecular weight was 280,000.

[0196] (Emulsion Production Example 3) An acrylic resin emulsion (hereinafter referred to as Emulsion 3) was obtained by carrying out a reaction in the same manner as in Emulsion Production Example 1, except that the amount of t-dodecyl mercaptan was 20 parts. The solid content of Emulsion 3 was 55%, and the Tg of the emulsion particles contained in Emulsion 3 was 3°C, the average particle size was 200 nm, and the weight-average molecular weight was 70,000.

[0197] (Emulsion Production Example 4) An acrylic resin emulsion (hereinafter referred to as Emulsion 4) was obtained by carrying out a reaction in the same manner as in Emulsion Production Example 1, except that the monomer components used were changed to 250 parts of butyl acrylate, 490 parts of styrene, 240 parts of 2-ethylhexyl acrylate, and 20 parts of acrylic acid. The solids content of Emulsion 4 was 55%, and the Tg of the emulsion particles contained in Emulsion 4 was −6° C., the average particle size was 200 nm, and the weight-average molecular weight was 250,000.

[0198] (Emulsion Production Example 5) Eliter KT-0507 (polyester resin emulsion) manufactured by Unitika (hereinafter referred to as Emulsion 5) was prepared. The solid content of Emulsion 5 was 25%, and the Tg of the emulsion particles contained in Emulsion 5 was −21° C., the average particle diameter was 150 nm, and the weight-average molecular weight was 55,000.

[0199] (Emulsion Production Example 6) Eliter KT-9204 (polyester resin emulsion) manufactured by Unitika (hereinafter referred to as Emulsion 6) was prepared. The solid content of Emulsion 6 was 30%, and the Tg of the emulsion particles contained in Emulsion 6 was 22°C, the average particle diameter was 150 nm, and the weight-average molecular weight was 70,000.

[0200] (Emulsion Production Example 7) A flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser was charged with 252 parts of deionized water. A pre-emulsion for dropping, consisting of 437 parts of deionized water, 80 parts of a 25% aqueous solution of an emulsifier (manufactured by ADEKA Corporation, trade name: ADEKA REASORB SR-10), 25 parts of acrylic acid, 565 parts of 2-ethylhexyl acrylate, 50 parts of cyclohexyl methacrylate, 10 parts of hydroxyethyl methacrylate, and 350 parts of styrene, was prepared. 44 parts, or 3% of the total amount of the pre-emulsion for dropping, was added to the dropping funnel. The temperature was raised to 80°C while slowly blowing in nitrogen gas, and 30 parts of a 5% aqueous solution of ammonium persulfate was added to initiate polymerization. The remainder of the pre-emulsion for dropping and 30 parts of a 5% aqueous solution of ammonium persulfate were then uniformly added dropwise to the flask over 240 minutes. After the dropwise addition was completed, the contents of the flask were maintained at 80°C for 180 minutes, and then 25% aqueous ammonia and deionized water were added to adjust the pH to 8.5 and the solids content to 50%, thereby terminating the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire screen to obtain an acrylic resin emulsion (hereinafter referred to as Emulsion 7). The solids content of Emulsion 7 was 50%, and the Tg of the emulsion particles contained in Emulsion 7 was -21°C, the average particle size was 200 nm, and the weight-average molecular weight was 1,100,000.

[0201] (Emulsion Production Example 8) Eliter KT-8803 (polyester resin emulsion) manufactured by Unitika (hereinafter referred to as emulsion 8) was prepared. The solid content of emulsion 8 was 30%, and the Tg of the emulsion particles contained in emulsion 8 was 66°C, the average particle diameter was 100 nm, and the weight average molecular weight was 50,000.

[0202] (Emulsion Production Example 9) An acrylic resin emulsion (hereinafter referred to as Emulsion 9) was obtained by carrying out a reaction in the same manner as in Emulsion Production Example 1, except that the amount of t-dodecyl mercaptan was 60 parts. The solid content of Emulsion 9 was 55%, and the Tg of the emulsion particles contained in Emulsion 9 was 2°C, the average particle size was 200 nm, and the weight-average molecular weight was 7,000.

[0203] (Emulsion Production Example 10) An acrylic resin emulsion (hereinafter referred to as emulsion 10) was obtained by carrying out a reaction in the same manner as in emulsion production example 1, except that the monomer components used were changed to 498 parts of methyl methacrylate, 498 parts of butyl acrylate, and 4 parts of acrylic acid. The solid content of emulsion 10 was 50%, and the Tg of the emulsion particles contained in emulsion 10 was 10°C, the average particle size was 200 nm, and the weight-average molecular weight was 300,000.

[0204] (Emulsion Production Example 11) An acrylic resin emulsion (hereinafter referred to as emulsion 11) was obtained by carrying out a reaction in the same manner as in emulsion production example 1, except that the monomer components used were changed to 500 parts of methyl methacrylate and 500 parts of butyl acrylate. The solid content of emulsion 11 was 50%, and the Tg of the emulsion particles contained in emulsion 11 was 10°C, the average particle diameter was 200 nm, and the weight average molecular weight was 300,000.

[0205] The methods for measuring the Tg, average particle size, weight average molecular weight, etc. of each emulsion particle in Production Examples 1 to 11 are as follows.

[0206] (Measurement of Tg of emulsion particles) The glass transition temperature (Tg) of the emulsion particles was measured by differential scanning calorimetry (DSC) under the following measurement conditions. Measuring equipment: DSC 3500 (product name, manufactured by NETZSCH) Sample container: Aluminum airtight container Sample weight: 10mg±2mg Measurement method: In a N2 atmosphere, two cycles of temperature increase from -50°C to 150°C were performed. The temperature increase and 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 heating cycle, and the midpoint glass transition temperature was used.

[0207] (Measurement of the average particle size of emulsion particles) The average particle size (volume basis) of the emulsion particles was measured using the emulsion obtained in each production example as a measurement sample with a particle size distribution analyzer (Otsuka Electronics Co., Ltd., product number: FPAR-1000) by dynamic light scattering, and was determined using cumulant analysis.

[0208] (Measurement of weight-average molecular weight of emulsion particles) The weight average molecular weight (Mw) of the emulsion particles was measured by GPC (gel permeation chromatography) under the following measurement conditions. Measuring equipment: HLC-8320GPC (product name, manufactured by Tosoh Corporation) Molecular weight column: TSK-GEL SuperMultiporeHZ (Tosoh Corporation) Eluent: tetrahydrofuran (THF) Standard material for calibration curve: Polystyrene (manufactured by Tosoh Corporation) Measurement method: The substance to be measured was dissolved in THF so that the solid content was approximately 0.2% by mass, and the resultant was filtered to measure the molecular weight. The flow rate of the liquid delivery pump was 0.35 ml / min.

[0209] (Pigment Dispersion Production Example 1) A mixture of 5 parts Discoat N-14 (Dai-ichi Kogyo Seiyaku) dispersant, 6 parts propylene glycol, 70 parts deionized water, 100 parts CR-95 titanium dioxide (Ishihara Sangyo Kaisha), and 0.5 mm particle size zirconia beads was filled at a volume ratio of 50%, dispersed using a bead mill, and filtered through a 1 μm pore size filter (Advantec Co., Ltd., MCP-1-C10S) to obtain a 55% pigment white pigment dispersion (hereinafter referred to as Pigment Dispersion 1). The average particle size of the pigment was 330 nm.

[0210] (Pigment Dispersion Production Example 2) Three parts of the dispersant Joncryl 678 (BASF), 1.3 parts of dimethylaminoethanol, and 81 parts of deionized water were mixed and stirred at 70°C. Next, 15 parts of the blue pigment CI Pigment Blue 15:3 LIONOL BLUE FG-7330 (Toyo Ink), 0.1 parts of the surfactant Olfin D-10PG (Nissin Chemical Industry), and 0.5 mm particle size zirconia beads were added to a 50% volumetric filling, dispersed using a bead mill, and filtered through a 1 μm pore size filter (Advantec, MCP-1-C10S) to obtain a 15% blue pigment dispersion (hereinafter referred to as Pigment Dispersion 2). The average particle size of the pigment was 90 nm.

[0211] (Measurement of the average particle size of pigments) The average particle size (volume basis) of the pigment described above was determined by measuring the pigment dispersion obtained in each production example as a measurement sample using a particle size distribution measuring instrument (manufactured by Otsuka Electronics Co., Ltd., product number: FPAR-1000) based on the dynamic light scattering method, and then by cumulant analysis.

[0212] (Preparation of White Ink) A white ink was produced by mixing 30 parts of Emulsion 7 (15 parts as emulsion particles), 23 parts of Pigment Dispersion 1, 1.2 parts (0.3 parts as solids) of Epocross WS-700 (manufactured by Nippon Shokubai Co., Ltd., solids content 25%), 2 parts of diethylene glycol monobutyl ether, 15 parts of triethylene glycol, 0.3 parts of surfactant KF-6011 (manufactured by Shin-Etsu Chemical Co., Ltd., polyether-modified silicone surfactant), and 28.5 parts of deionized water and filtering the mixture through a 1 μm pore size filter (manufactured by Advantec, MCP-1-C10S).

[0213] (Preparation of cyan ink) A cyan ink was produced in the same manner as in the preparation of the white ink, except that Pigment Dispersion 1 was changed to Pigment Dispersion 2.

[0214] (Preparation of Adhesive Ink 1) A total of 100 parts of emulsion 1 (25 parts emulsion particles), diethylene glycol monobutyl ether 2 parts, triethylene glycol 15 parts, surfactant KF-6011 (Shin-Etsu Chemical Co., Ltd.) 0.6 parts, and deionized water 36.9 parts were mixed and filtered through a 1 μm pore size filter (Advantec, MCP-1-C10S) to produce adhesive ink 1.

[0215] (Preparation of Adhesive Inks 2 to 17) Adhesive inks 2 to 17 were produced in the same manner as in preparing adhesive ink 1, except that the type and amount of each raw material used were changed as shown in Table 1 and deionized water was added in an amount to make the total amount 100 parts. Note that "Surfynol 440" in Table 1 is the trade name of an acetylene glycol surfactant manufactured by Evonik.

[0216] [Table 1]

[0217] [Devices used and transfer substrate] (Inkjet ejection device) Two Mastermind printers (MMP-TX13) were prepared, designated Printer A and Printer B. A rubber heater was installed on the platen of each printer, and the printers were heated to 50°C. Printer A was filled with cyan ink and white ink, which are colored inks. Printer B was filled with adhesive ink and cyan ink, which is a colored ink.

[0218] [Examples 1 to 22, Comparative Examples 1 to 5] The ink prepared above was used to carry out the following printing process through transfer process, and various properties were evaluated. The results are shown in Tables 2 to 4.

[0219] (Printing process) The transfer substrate was placed on a rubber heater, and an image was formed by the inkjet method. When using white ink, a solid print (8 × 16 cm) was made using cyan ink using printer A. 2 ) and then print solid white ink on it (8 x 16 cm 2 The printed transfer substrate was transferred to printer B, and a solid print (8 × 16 cm) was printed on it with adhesive ink. 2 When white ink was not used, a solid print (8 x 16 cm) was made using printer B with cyan ink. 2 ) and then printed solidly with adhesive ink (8 x 16 cm 2 The amount of colored ink ejected per unit area was 70 g / m 2 The transfer substrate was a PET film having an ink-receiving layer on one side, and the image was formed on the ink-receiving layer side.

[0220] (drying process) The substrate on which the image was formed was dried for 5 minutes in a hot air dryer at 130° C. to prepare a transfer medium. The thickness of the adhesive ink layer shown in Tables 2 to 4 was measured by cutting the obtained transfer medium and observing the cross section of the adhesive ink layer using a VHX-8000 series digital microscope (manufactured by Keyence Corporation). The thickness of the adhesive ink layer was adjusted by appropriately changing the amount of adhesive ink ejected and the number of prints in the above printing process.

[0221] (Transfer process) -Transfer process in Examples 1 to 20 and Comparative Examples 1 to 3- A transfer press machine TP-630M manufactured by Horizon International was used. The heating temperature was 150°C, and the press load was 3 kN (transfer pressure: 400 g / cm). 2 ) was set. The fabric, which served as the transfer medium, was placed on the lower iron, and the transfer medium was then placed on top of that with the print side facing down and stamped for 10 seconds. After stamping, once the fabric temperature had dropped to below 40°C, the transfer substrate was peeled off from the fabric to obtain a printed item. The resulting printed item was then placed again on the lower iron, silicone release paper was placed on top of the printed item, and stamped for 5 seconds to press the image onto the fabric. -Transfer process in Examples 21 and 22 and Comparative Examples 4 and 5- A transfer press machine TP-630M manufactured by Horizon International was used. The heating temperature was 150°C, and the press load was 3 kN (transfer pressure: 400 g / cm). 2 ) was set. The fabric, which was the medium for transfer, was placed on the lower iron, and the transfer medium was placed on top of that with the print side facing down, and stamped for 3 seconds. After stamping, once the temperature of the fabric had dropped to 40°C or less, the transfer substrate was peeled off from the fabric, and a printed item was obtained.

[0222] In the above transfer process, a 100% cotton white T-shirt manufactured by Hanes was used as the cotton fabric, a 100% polyester white T-shirt manufactured by Cab Corporation (product number: 5900-01) was used as the polyester fabric, and a 100% nylon coyote jacket manufactured by Cab Corporation (product number: 7059-01) was used as the nylon fabric.

[0223] [Characteristics evaluation] (1) Transferability evaluation The transfer substrate obtained in each example and comparative example after the transfer process was evaluated as "x" if the image printed by the inkjet printer remained on it, and as "o" if no image remained on it.

[0224] (2) Evaluation of the texture of printed items The printed textiles obtained in each Example and Comparative Example were evaluated by touch. Printed textiles that felt stiff were rated as x, while printed textiles that easily bent and had a softness close to that of the fabric itself were rated as o. Note that in Comparative Examples 1, 4, and 5, it was not possible to transfer all of the inks, and therefore it was not possible to evaluate the texture of the printed textiles.

[0225] (3) Evaluation of wet rub fastness of printed textiles The printed textiles obtained in each Example and Comparative Example were subjected to a wet rub test in accordance with the method specified in JIS L0849 using a type II testing machine with a cotton No. 3-1 white cloth attached, with a load of 200 g and 100 strokes, and evaluated using a discoloration gray scale. Note that in Comparative Examples 1, 4, and 5, it was not possible to transfer all of the ink, and therefore it was not possible to evaluate the wet rub fastness of the printed textiles. ◎: Wet friction test contamination is grade 4-5 or higher ○: Wet friction test contamination is grade 3-4 or grade 4 △: Wet friction test contamination is grade 2-3 or grade 3 ×: Wet friction test contamination is grade 2 or less

[0226] (4) Evaluation of washing fastness of printed fabrics The printed fabrics obtained in each of the Examples and Comparative Examples were washed by repeating the cycle of "washing → rinsing → spin-drying" five times in succession under the following conditions, and the fabrics obtained after the fifth spin-drying were used as samples. Washing machine: Model number NA-F5B1 (Panasonic) ·Water volume: 32L Course: Select 1 rinse Detergent: Ariel Liquid Laundry Detergent with Disinfectant Plus (P&G), 35g The washing fastness of the samples obtained by the above method was evaluated based on the rate of fabric exposure due to cracking or peeling of the print. The exposure rate was determined by printing the surface of the sample (transfer-printed area) with a copier, and then using an image processing device, determining the ratio of the area of ​​the exposed fabric to the area of ​​the transfer-printed area, and the resulting value was taken as the exposure rate. In Comparative Examples 1, 4, and 5, it was not possible to transfer all of the ink, so it was not possible to evaluate the washing fastness of the printed textile. ◎: Fabric exposure rate is 0.1% or less ○: Fabric exposure rate is over 0.1% and 2.0% or less △: Fabric exposure rate is over 2.0% and 4.0% or less ×: Fabric exposure rate exceeds 4.0%

[0227] (5) Evaluation of yellowing of adhesive ink layer The adhesive ink layer on the transfer medium obtained after the above (drying process) was visually inspected, and if no yellowing of the adhesive ink layer was observed, it was evaluated as "none", and if yellowing of the adhesive ink layer was observed, it was evaluated as "yes".

[0228] [Table 2]

[0229] [Table 3]

[0230] [Table 4]

[0231] In Examples 1 to 22, in which the glass transition temperature and weight average molecular weight of the resin contained in the adhesive ink were adjusted to fall within the specified ranges, the inks exhibited excellent transferability during transfer printing onto fabrics, and the resulting printed textiles exhibited excellent wet rub fastness and texture. [Explanation of symbols]

[0232] 100 Transfer Media 1 Transfer substrate 2 Colored ink layer 3 Adhesive ink layer 4. Ink-receiving layer 5 Release layer 6 Fabric

Claims

1. An inkjet adhesive ink used for transfer printing onto fabric, comprising: the adhesive ink contains a resin, a water-soluble organic solvent, and water; The resin contains an acrylic resin, has a glass transition temperature of 30° C. or less, and has a weight average molecular weight of 10,000 to 700,000.

2. The adhesive ink of claim 1 , wherein the resin is contained in the adhesive ink as emulsion particles.

3. The adhesive ink of claim 1 , wherein the fabric is formed from cotton, polyester fibers, polypropylene fibers, nylon fibers, or mixtures thereof.

4. An adhesive ink as described in claim 1, wherein the weight average molecular weight of the resin is 30,000 or more.

5. An adhesive ink as described in claim 1, wherein the acrylic resin contains structural units derived from an acid group-containing monomer.

6. An adhesive ink as described in claim 5, wherein the content of structural units derived from the acid group-containing monomer is 0.1 to 5 mass % relative to 100 mass % of the total structural units derived from all monomers constituting the acrylic resin.

7. An adhesive ink as described in claim 1, wherein the content of the acrylic resin is 65 mass% or more out of 100 mass% of the resin contained in the adhesive ink.

8. The adhesive ink of claim 1; and a colored ink containing a pigment and a resin.

9. The ink set described in Claim 8, wherein the resin contained in the colored ink includes an acrylic resin.

10. A transfer medium comprising a transfer substrate on which the adhesive ink according to claim 1 is printed, with or without a colored ink layer formed from a colored ink containing a pigment and a resin.

11. The transfer medium according to claim 10 , wherein the transfer substrate is a plastic film or paper.

12. The transfer medium according to claim 10 , further comprising an ink-receiving layer on the surface of the transfer substrate on which the adhesive ink is printed.

13. A printed textile that is transfer printed using the adhesive ink according to claim 1.

14. Step 3: printing an adhesive ink by inkjet onto a transfer substrate or onto a colored ink layer laminated on the transfer substrate; and Step 4: drying the adhesive ink; the adhesive ink used in step 3 contains a resin, a water-soluble organic solvent, and water, the resin contains an acrylic resin, has a glass transition temperature of 30°C or less, and has a weight average molecular weight of 10,000 to 700,000; A method for manufacturing a transfer medium for transfer printing onto fabric.

15. The step 3 is a step of printing an adhesive ink by inkjet printing onto a colored ink layer laminated on a transfer substrate, The manufacturing method according to claim 14, wherein the colored ink layer is formed by step 1 of printing colored inks on a transfer substrate by inkjet printing, and step 2 of drying the colored inks.

16. The manufacturing method according to claim 15, wherein the step 2 is a step of evaporating 20 to 80% by mass of 100% by mass of the components excluding solid content of the color ink.

17. The manufacturing method according to claim 14, wherein the thickness of the adhesive ink is 0.5 to 200 μm after the drying step 4.

18. A method for producing a printed item, comprising a step of transferring and printing the transfer medium obtained by the production method according to claim 14 onto a fabric.

19. the transfer printing step includes a contact step of bringing the surface of the transfer medium, on which the adhesive ink is printed, into close contact with the fabric while facing the fabric, and a step of peeling the transfer substrate from the fabric, The method according to claim 18 , wherein the adhesion time in the adhesion step is 30 seconds or less.

Images