Adhesive ink, and method for manufacturing printed materials using the adhesive ink

Abstract

The objective is to provide an adhesive ink that exhibits excellent transferability during transfer printing on woven fabrics, and that can enhance the wet abrasion fastness and texture of the resulting printed material. [Solution] The above problem can be solved by providing an adhesive ink that contains a resin, a water-soluble organic solvent, and water, wherein the resin has a glass transition temperature of 30°C or less and a weight-average molecular weight of 10,000 to 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 material transferred using the adhesive ink. [Background technology]

[0002] Conventionally, a method is known in which characters or images formed by printing colored ink onto a transfer substrate are transferred to a transfer medium. For example, Patent Document 1 describes that a transfer medium obtained by a method including a colored layer formation step of ejecting ink from an inkjet head toward a substrate to form a colored layer on the substrate, and an adhesive layer formation step of ejecting an adhesive liquid from an inkjet head toward the colored layer to form an adhesive layer on the colored layer, exhibits excellent transferability to transfer mediums such as plastics.

[0003] Furthermore, Patent Document 2 describes an aqueous hot melt adhesive ink for digital textile printing, stating that by adjusting the amounts of aqueous hot melt adhesive resin, aqueous curing agent, humectant, surfactant, defoamer, antiseptic, pH adjuster, and deionized water, an adhesive ink that can be applied to inkjet printing and has good adhesive strength, water resistance, and flexibility can be provided. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2012-126026 [Patent Document 2] Chinese Patent Application Publication No. 111117360 Specification [Overview of the project] [Problems that the invention aims to solve]

[0005] In transfer printing, not only excellent transferability is required, but when the transfer medium is fabric, it is also required that the resulting dyed product (the fabric printed by transfer printing) has good wet rubbing fastness and texture. However, in Patent Document 1, no aspect where the transfer medium is fabric has been studied at all. Further, although Patent Document 2 describes transfer printing where the transfer medium is fabric, the studies on transferability, wet rubbing fastness, and texture are insufficient.

[0006] Therefore, an object of the present invention is to provide an adhesive ink, an ink set, and a transfer medium that are excellent in transferability during transfer printing onto fabric and can enhance the wet rubbing fastness and texture of the resulting dyed product. [Means for Solving the Problems]

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that by adjusting the balance between the glass transition temperature and the weight average molecular weight of the resin contained in the adhesive ink, it is excellent in transferability during transfer printing onto fabric and can enhance the wet rubbing fastness and texture of the resulting dyed product, and have thus completed the present invention.

[0008] That is, the present invention is as follows. [1] An adhesive ink for inkjet used for transfer printing onto fabric, wherein the adhesive ink 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. [2] The adhesive ink according to [1], wherein the resin contains at least one selected from the group consisting of an acrylic resin and a polyester resin. [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] An ink set comprising the adhesive ink according to any one of [1] to [4], and a coloring ink containing a pigment and a resin. [6] The resin contained in the adhesive ink includes at least one selected from the group consisting of an acrylic resin and a polyester resin, and the resin contained in the coloring ink includes at least one selected from the group consisting of an acrylic resin and a polyester resin. The ink set according to [5]. [7] A transfer medium in which the adhesive ink according to any one of [1] to [4] is printed on a transfer substrate, either via or without a coloring ink layer formed from a coloring 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], wherein the transfer medium further has an ink receiving layer on the surface of the transfer substrate where the adhesive ink is printed.

[10] A resist-dyed article obtained by transfer printing using the adhesive ink according to any one of [1] to [4].

[11] Step 3: Printing an adhesive ink by inkjet on a transfer substrate or on a coloring ink layer laminated on the transfer substrate; and, Step 4: Drying the adhesive ink; are included, The adhesive ink used in Step 3 includes 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 a fabric.

[12] The manufacturing method according to

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

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

[11] or

[12] , wherein the colored ink layer is formed by a step 1 of printing colored ink onto a transfer substrate using an inkjet printer, and a step 2 of drying the colored ink.

[14] The manufacturing method according to

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

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

[14] , wherein the resin contained in the colored ink comprises 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 step 2 is a step of evaporating 20 to 80% by mass of 100% by mass of the components of the colored ink excluding the solid components.

[17] The manufacturing method according to any one of

[11] to

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

[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 manufacturing 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 performed on (I) an ink receiving layer laminated on a transfer substrate, or (II) the side of the colored ink layer in a laminate in which the transfer substrate, ink receiving layer, and colored ink layer are laminated in that order. A method for producing a printed fabric, comprising the step of transferring a transfer medium obtained by any of the manufacturing methods described in

[11] to

[20] onto a cloth.

[22] The transfer printing process comprises an adhesion step of bringing the side of the transfer medium on which adhesive ink is printed into close contact with the fabric, and a step of peeling the transfer substrate from the fabric. The manufacturing method according to

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

[23] The method for manufacturing the fabric according to

[21] or

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

[0009] According to the present invention, it is possible to provide an adhesive ink that exhibits excellent transferability during transfer printing on fabrics and that can improve the wet friction fastness and texture of the resulting printed material. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic cross-sectional view showing an example of the layered structure of the transfer medium in the present invention. [Figure 2] This is a schematic cross-sectional view showing another example of the layered structure of the transfer medium in the present invention. [Figure 3] This is a schematic cross-sectional view showing yet another example of the layered structure of the transfer medium in the present invention. [Figure 4] This is a schematic cross-sectional view showing an example of a laminated structure of a transfer medium and fabric during transfer printing according to the present invention. [Modes for carrying out the invention]

[0011] One embodiment of the present invention will be described below, but the present invention is not limited thereto. Unless otherwise specified in this specification, "A~B" representing a numerical range means "A or more, B or less". Also, "(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, "~derived structural unit" 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 (-CC-)).

[0012] 1. Adhesive ink The adhesive ink of the present invention is an inkjet adhesive ink used for transfer printing onto fabrics, wherein the adhesive ink comprises a resin, a water-soluble organic solvent, and water, and the resin is characterized by having a glass transition temperature of 30°C or less and a weight-average molecular weight of 10,000 to 700,000. In addition to the components described above, the adhesive ink of the present invention may also contain other components as needed. The components constituting the adhesive ink of the present invention will now be described.

[0013] <Resin> The adhesive ink of the present invention contains a resin. 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 to the above range, the texture of the resulting printed material is excellent. Furthermore, by adjusting the Tg of the resin to the above range and adjusting the weight-average molecular weight of the resin to 10,000 to 700,000, the transferability during transfer printing and the wet friction fastness of the resulting printed material 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 stored wound in a roll, and in this case, blocking by the adhesive ink may be a problem. By adjusting the lower limit of the Tg of the resin to the above range, such blocking can be suppressed. In other words, the Tg of the resin is preferably -50 to 30°C, more preferably -30 to 20°C, even more preferably -20 to 15°C, and particularly preferably -10 to 10°C.

[0015] The glass transition temperature (Tg) of a resin can be determined by differential scanning calorimetry (DSC). Specifically, for example, using a differential scanning calorimetry analyzer (NETZSCH's "DSC 3500"), the resin is heated and cooled in the following steps to create a DSC curve, and the midpoint glass transition temperature obtained from the DSC curve during the second heating step is taken as the glass transition temperature (Tg) of the resin. (Step 1) Increase the temperature from -50°C to 150°C at a rate of 10°C / min, and hold at 150°C for 5 minutes. (Step 2) Cool the temperature from 150°C to -50°C at a rate of 10°C / min, and hold at -50°C for 5 minutes. (Step 3) Heat from -50°C to 150°C at a rate of 10°C / min.

[0016] In cases where the resin takes on a core-shell structure, multiple glass transition temperatures may be observed. In such cases, it is sufficient if at least one of the glass transition temperatures satisfies the above range, but it is preferable that all glass transition temperatures satisfy the above range. Furthermore, when using two or more types of resin, it is preferable that the Tg of the main component resin satisfies the above range, and it is even more preferable that the Tg of each of the resins is within the above range. The main component resin refers to the resin that accounts for preferably 50% or more by mass, more preferably 60% or more by mass, even more preferably 80% or more by mass, and particularly preferably 90% or more by mass, of the total 100% by mass of 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 to the above range, it is possible to suppress the flow of the adhesive ink after printing. Alternatively, the weight-average molecular weight of the resin may be 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 to the above range and adjusting the Tg of the resin to 30°C or less, the transferability during transfer printing and the wet friction fastness of the resulting printed material are excellent. In other words, 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 also be 30,000 to 350,000 or 50,000 to 300,000.

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

[0019] When using two or more types of resins, it is sufficient if the weight-average molecular weight of the resins as a mixture satisfies the above range, but it is preferable that the weight-average molecular weight of each of the resins is within the above range.

[0020] The type of resin contained in the adhesive ink of the present invention is not particularly limited, and examples include vinyl resins, acrylic resins, polyester resins, olefin resins, urethane resins, fluororesins, silicone resins, epoxy resins, phenoxy resins, phenolic resins, xylene resins, etc., among which acrylic resins and / or polyester resins are 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 subjected to heating during the manufacture of the transfer medium or printed material, as described later, and this heating may cause the resulting adhesive ink layer to yellow. Suppressing such yellowing is sometimes required to improve the design quality of the resulting printed material, and by using an acrylic resin as the resin, the above-mentioned yellowing can be suppressed.

[0021] The acrylic resin is a resin containing structural units derived from (meth)acrylic monomers. The content of structural units derived from (meth)acrylic monomers, relative to 100% by mass of the total 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 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 structural units derived from (meth)acrylic monomers to the above range, the wet friction fastness of the resulting printed material is further improved, and the yellowing of the adhesive ink layer in the printed material tends to be further suppressed.

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

[0023] Examples of the monofunctional (meth)acrylate include: (Meth)acrylic acid, (meth)acrylic acid salts (hereinafter collectively referred to as (meth)acrylic acid (salt)); 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, stearyl (meth)acrylate), and cyclic alkyl (meth)acrylates (e.g., cyclohexyl (meth)acrylate, 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 tripoxy (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)acryloxylpropyl propenal, 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 aziridinyl groups, such as (meth)acryloylaziridine and 2-aziridinylethyl (meth)acrylate; Oxo group-containing (meth)acrylates such as ethylene glycol (meth)acrylate, ethylene glycol methoxy (meth)acrylate, diethylene glycol (meth)acrylate, diethylene glycol methoxy (meth)acrylate, and other (di)ethylene glycol (methoxy) (meth)acrylates; 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; one or more of these can be selected and used.

[0024] Examples of salts of (meth)acrylic acid include alkali metal salts of (meth)acrylic acid and ammonium salts of (meth)acrylic acid. Examples of alkali metals constituting the alkali metal salt include lithium, sodium, and potassium. The ammonium component of the ammonium salt is NH4 + It may be a tetraalkylammonium compound, or it may be an organic ammonium compound. Examples of organic ammonium compounds include tetramethylammonium, tetrabutylammonium, and other tetraalkylammonium compounds (preferably tetraC). 1-10Alkylammonium), trialkylammonium such as trimethylammonium, triethylammonium, tributylammonium (preferably tri-C 1-10 Alkylammonium), hydroxyalkylammonium such as monoethanolammonium, diethanolammonium, triethanolammonium (preferably mono-, di- or tri-(hydroxy-C 1-10 Alkyl)ammonium), dialkylmonohydroxyalkylammonium such as dimethylmonoethanolammonium (preferably di-C 1-10 Alkylmono(hydroxy-C 1-10 Alkyl)ammonium), etc. are mentioned.

[0025] Among them, as the monofunctional (meth)acrylate, it is preferable to contain (meth)acrylic acid (salt) and / or alkyl (meth)acrylate, more preferably to contain at least alkyl (meth)acrylate, still more preferably to contain (meth)acrylic acid (salt) and alkyl (meth)acrylate.

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

[0027] As the alkyl (meth)acrylate, it is preferable to contain an alkyl (meth)acrylate having 1 to 18 carbon atoms in the alkyl group (hereinafter referred to as C 1-18 Alkyl (meth)acrylate), and more preferably to contain C 4-12 Alkyl (meth)acrylate. Also, as the above alkyl (meth)acrylate, it is also a preferable form to use two or more kinds having different carbon numbers in combination. For example, C 1-3 Alkyl (meth)acrylate and C4-18 Forms used in combination with alkyl (meth)acrylate, C 4-6 Alkyl (meth)acrylate and C 7-18 Forms used in combination with alkyl (meth)acrylate, C 1-3 Alkyl (meth)acrylate and C 4-6 Alkyl (meth)acrylate and C 7-18 Examples include forms used in combination with alkyl (meth)acrylates.

[0028] The content of monofunctional (meth)acrylate-derived structural units (preferably the total content of (meth)acrylic acid (salt)-derived structural units and alkyl (meth)acrylate-derived structural units) relative to 100% by mass of the total 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 also be 70% by mass or more or 80% by mass or more, and may also 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 also 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 2 to 50 moles of alkylene oxide groups with 2 to 4 carbon atoms, such as polyethylene glycol di(meth)acrylate with 2 to 50 moles of ethylene oxide added, polypropylene glycol di(meth)acrylate with 2 to 50 moles of propylene oxide added, 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 with 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 with 1 to 10 carbon atoms, such as pentaerythritol penta(meth)acrylate and dipentaerythritol (monohydroxy)penta(meth)acrylate; Hexa(meth)acrylates of polyhydric alcohols with 1 to 10 carbon atoms, such as pentaerythritol hexa(meth)acrylate; Epoxy group-containing (meth)acrylates such as bisphenol A di(meth)acrylate, 2-(2'-vinyloxyethoxyethyl)(meth)acrylate, and epoxy(meth)acrylate; Examples include polyfunctional (meth)acrylates such as urethane (meth)acrylates; and one or more types can be selected and used.

[0030] The content of structural units derived from polyfunctional (meth)acrylates relative to 100% by mass of the total structural units derived from all monomer components constituting the acrylic resin 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 structural units derived from acid group-containing monomers. The inclusion of structural units derived from acid group-containing monomers in the acrylic resin improves its stability. The structural units derived from acid group-containing monomers may be present in the acrylic resin alone or in two or more types.

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

[0033] When an 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 (salt)) relative to 100% by mass of the total 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, and even more preferably 1.0% by mass or more, and also 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 even more preferably 1.0 to 3% by mass. Furthermore, from the viewpoint of improving the wash fastness of the resulting printed material, the content of structural units derived from acid group-containing monomers (preferably the content of structural units derived from (meth)acrylic acid (salt)) relative to 100% by mass of the total structural units derived from all monomer components constituting the acrylic resin is preferably 0 to 3% by mass, more preferably 0 to 1% by mass, even more preferably 0 to 0.5% by mass, even 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 contain structural units derived from styrene monomers. The total content of structural units derived from (meth)acrylic monomers and styrene monomers (preferably the total content of structural units derived from (meth)acrylic acid (salt), alkyl (meth)acrylate, and styrene monomers) relative to 100% by mass of the total 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, even more preferably 95% by mass or more, and may be 100% by mass.

[0035] Examples of the styrene monomers mentioned above include styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, vinyltoluene, 2-styrylethyltrimethoxysilane, and divinylbenzene, and one or more of these can be selected and used. The styrene monomers may have functional groups such as methyl groups, alkyl groups such as tert-butyl groups, nitro groups, nitrile groups, alkoxyl groups, acyl groups, sulfone groups, hydroxyl groups, and halogen atoms on the benzene ring constituting the styrene monomers mentioned above. Among the styrene monomers, styrene is preferred from the viewpoint of improving water resistance.

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

[0037] In particular, the acrylic resin is a styrene monomer and / or C 1-3 Structural units derived from linear alkyl methacrylates, and C 4-12 Preferably, it contains structural units derived from linear alkyl acrylates, C 1-3 Structural units derived from linear alkyl methacrylates, and C 4-12 It is more preferable to include structural units derived from linear alkyl acrylates. In addition to these structural units, it is even more preferable to include structural units derived from acid group-containing monomers (preferably (meth)acrylic acid (salt)). Styrene monomers and C, relative to 100% by mass of structural units derived from all monomer components constituting the acrylic resin. 1-3 Chain-like alkyl methacrylate, C 4-12The total content of linear alkyl acrylates and structural units derived from acid group-containing monomers 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 4-12 The content of structural units derived from linear alkyl acrylates can be adjusted as appropriate depending on the target Tg, but is preferably 20 to 90% by mass, more preferably 30 to 75% by mass, and even more preferably 40 to 60% by mass. Styrene monomers and C 1-3 The total content of structural units derived from linear 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, per 100 parts by mass of structural units derived from linear alkyl acrylate. The content of structural units derived from acid group-containing monomers is styrene monomers, C 1-3 Chain-like 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, per 100 parts by mass of the total structural units derived from the linear 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 aforementioned other monomers are not particularly limited as long as they have at least one polymerizable unsaturated group in the molecule, but examples 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 monomers such as (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, and N,N-dimethyl(meth)acrylamide; olefin monomers such as ethylene and propylene; and the like.

[0040] The above-mentioned acrylic resin can be produced by conventionally known polymerization methods, such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. Among these, emulsion polymerization is preferred. Specifically, the above-mentioned acrylic resin is preferably produced by emulsion polymerization of the aforementioned monomer components ((meth)acrylic monomers, and optionally styrene 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, "monomer component" refers to a compound having at least one polymerizable unsaturated group in its molecule, other than the reactive emulsifier described later. The specific means and conditions for carrying out emulsion polymerization can be appropriately selected and adopted from conventionally known emulsion polymerization methods.

[0041] The emulsifier used in the emulsion polymerization described above is not limited to nonionic emulsifiers, anionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, polymer emulsifiers, etc., and conventionally known emulsifiers can be used. These emulsifiers may be used individually or in combination of two or more types. Among the above emulsifiers, nonionic emulsifiers and / or anionic emulsifiers are preferred. Emulsifiers containing polymerizable groups in their molecules (hereinafter sometimes referred to as reactive emulsifiers) are also preferred. Among the above 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 described above is not particularly limited, but is for example 10 to 80% by mass, and 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 alkyldiphenyl ether disulfonate; alkylaryl sulfonate salts such as ammonium dodecylbenzene sulfonate and sodium dodecylnaphthalene sulfonate; polyoxyethylene alkyl sulfonate salts; polyoxyethylene alkyl ether sulfate salts; polyoxyethylene alkylaryl ether sulfate salts; dialkyl sulfosuccinates; and aryl sulfonic acid-formaldehyde. Examples include, but are not limited to, condensates; fatty acid salts such as ammonium laurylate and sodium stearate; sulfate esters or salts thereof having an allyl group, such as bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkyl sulfosuccinate salt, (meth)acrylate polyoxyethylene sulfonate salt, (meth)acrylate polyoxyethylene phosphate salt, and sulfonate salt of allyloxymethylalkyloxypolyoxyethylene; sulfate ester salts of allyloxymethyl alkoxyethyl polyoxyethylene; and polyoxyalkylene alkenyl ether sulfate ammonium salts.

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

[0044] Examples of polymer emulsifiers include, but are not limited to, poly(meth)acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl (meth)acrylates such as polyhydroxyethyl acrylate; and copolymers in which one or more monomers constituting these polymers are copolymerized components.

[0045] In this specification, a reactive emulsifier refers to a compound having a polymerizable unsaturated group, a hydrophilic group, and a hydrophobic group, and the polymerizable unsaturated group may be one or more. Examples of polymerizable unsaturated groups include groups having an ethylenically unsaturated double bond, specifically (meth)acryloyl groups, vinyl groups, allyl groups, and styryl groups. Examples of hydrophilic groups include groups known as emulsifiers (surfactants), such as anionic groups like sulfonic acid groups, phosphate groups, sulfate ester residues, and phosphate ester residues; and nonionic groups like polyether groups and ester groups. Examples of hydrophobic groups include groups known as emulsifiers (surfactants), such as alkyl groups (especially alkyl groups with about 8 to 40 carbon atoms), aryl group-containing hydrocarbon groups (especially hydrocarbon groups with about 12 to 40 carbon atoms that have a phenyl group), and polycyclic phenyl groups.

[0046] Examples of reactive emulsifiers include, Propenyl-alkyl sulfosuccinate salts, (meth)acrylate polyoxyethylene sulfonate salts, (meth)acrylate polyoxyethylene phosphate salts (e.g., Sanyo Chemical Industries, Ltd., product name: Eleminol RS-30, etc.), polyoxyethylene alkylpropenylphenyl ether sulfonate salts (e.g., Daiichi Kogyo Seiyaku Co., Ltd., product name: Aqualon HS-10, etc.), allyloxymethylalkyloxypolyoxyethylene sulfonate salts (e.g., Daiichi Kogyo Seiyaku Co., Ltd., product name: Aqualon KH-10, etc.), polyoxyethylene styrene-propenylphenyl ether sulfate ammonia Anionic emulsifiers having polymerizable groups such as methyl methyl ester (e.g., manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Aqualon AR-10, etc.), allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene sulfonate salt (e.g., manufactured by ADEKA Corporation, product name: Adekarya Soap SE-10, etc.), allyloxymethyl alkoxyethyl hydroxypolyoxyethylene sulfate salt (e.g., manufactured by ADEKA Corporation, product names: Adekarya Soap SR-10, SR-30, etc.), and bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt (e.g., manufactured by Nippon Emulsifier Co., Ltd., product name: Antox MS-60, etc.); Examples include, but are not limited to, nonionic emulsifiers having polymerizable groups such as polyoxyethylene styrene-propenylphenyl ether (e.g., manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aquaron AN-10), allyloxymethyl alkoxyethyl hydroxypolyoxyethylene (e.g., manufactured by ADEKA Corporation, trade name: Adekarya Soap ER-20), polyoxyethylene alkylpropenylphenyl ether (e.g., manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aquaron RN-20), and allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene (e.g., manufactured by ADEKA Corporation, trade name: Adekarya Soap NE-10); and others.

[0047] The amount of emulsifier used is not limited, but is 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, per 100 parts by mass of monomer component. Protective colloids may also be used alone or together with the emulsifier as needed. When a reactive emulsifier is used as an emulsifier, the polymerizable groups of the reactive emulsifier react during polymerization, resulting in the resin having structural units derived from the reactive emulsifier. The content of 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 structural units derived from the monomer component.

[0048] The polymerization initiators used in the emulsion polymerization described above are not limited to these examples, but include, for example, 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. However, the examples are not limited to these. These polymerization initiators may be used individually or in combination of two or more types.

[0049] The amount of polymerization initiator used when carrying out the above 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 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] Furthermore, the polymerization reaction may be carried out in the presence of a chain transfer agent in order to adjust the weight-average molecular weight of the resulting resin. 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 individually or in combination of two or more. The amount of chain transfer agent used may be adjusted as appropriate according to the desired weight-average molecular weight, but it is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of monomer component.

[0051] The reaction temperature and reaction time for the emulsion polymerization described above can be appropriately set considering the weight-average molecular weight of the target resin, the blending ratio of monomer components, and the type of polymerization initiator. However, the reaction temperature is, for example, 0 to 100°C, preferably 50 to 95°C, more preferably 60 to 90°C, and the reaction time is, for example, 0.5 to 30 hours, preferably 1 to 20 hours, more preferably 3 to 10 hours. The reaction pressure is also not particularly limited and may be normal pressure (atmospheric pressure), reduced pressure, or pressurized pressure. It is desirable to carry out the polymerization reaction under an atmosphere of an inert gas such as nitrogen gas.

[0052] Examples of aqueous solvents used in the emulsion polymerization described above include water and mixed solvents of water and water-soluble organic solvents. A water-soluble organic solvent is an organic solvent that dissolves in water at a concentration of 0.01% by mass or more at room temperature and atmospheric pressure. In this specification, room temperature means 25°C and atmospheric 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 water-soluble organic solvents 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 such as propylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol (preferably glycols); Trihydric alcohols such as glycerin; Monoethylene glycol ethers such as monoethylene glycol monomethyl ether, monoethylene glycol monoethyl ether, monoethylene glycol monopropyl ether, monoethylene glycol monoisopropyl ether, monoethylene glycol monobutyl ether, and monoethylene glycol monoisobutyl ether (preferably monoalkyl ethers of monoethylene glycol); Monopropylene glycol ethers 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); Diethylene glycol ethers 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 diethylene glycol monoalkyl ethers); Dipropylene glycol ethers 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 dipropylene glycol monoalkyl ethers); Polyethylene glycol ethers such as monomethyl ether of polyethylene glycol (number of EO added moles = 2 to 10, preferably 2 to 4), monoethyl ether of polyethylene glycol (number of EO added moles = 2 to 10, preferably 2 to 4), monopropyl ether of polyethylene glycol (number of EO added moles = 2 to 10, preferably 2 to 4), monoisopropyl ether of polyethylene glycol (number of EO added moles = 2 to 10, preferably 2 to 4), monobutyl ether of polyethylene glycol (number of EO added moles = 2 to 10, preferably 2 to 4), and monoisobutyl ether of polyethylene glycol (number of EO added moles = 2 to 10, preferably 2 to 4) (preferably, monoalkyl ether of polyethylene glycol); Polypropylene glycol ethers (preferably polypropylene glycol monoalkyl ethers), such as monomethyl ether of polypropylene glycol (number of PO added moles = 2 to 10, preferably 2 to 4), monoethyl ether of polypropylene glycol (number of PO added moles = 2 to 10, preferably 2 to 4), monopropyl ether of polypropylene glycol (number of PO added moles = 2 to 10, preferably 2 to 4), monoisopropyl ether of polypropylene glycol (number of PO added moles = 2 to 10, preferably 2 to 4), monobutyl ether of polypropylene glycol (number of PO added moles = 2 to 10, preferably 2 to 4), and monoisobutyl ether of polypropylene glycol (number of PO added moles = 2 to 10, preferably 2 to 4); Heterocyclic compounds such as 2-pyrrolidone and N-methyl-2-pyrrolidone; Examples include acetone, methyl ethyl ketone and other ketones; and so on.

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

[0055] The amount of aqueous solvent used when carrying out the above 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 monomer component.

[0056] Specific polymerization methods in the emulsion polymerization described above include, for example, monomer drop-in polymerization, pre-emulsion drop-in polymerization, seed polymerization, and multi-stage polymerization.

[0057] In the emulsion polymerization reaction system described above, appropriate amounts of additives such as pH buffers and chelating agents may be added as needed. The amount of additive varies depending on its type and cannot be determined definitively, but it 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 monomer components.

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

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

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

[0061] Examples of the aforementioned diol compounds 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 (2-4 carbon atoms) oxide (average number of added moles 1-16) adducts.

[0062] The aforementioned polyester resin may also contain an aliphatic polybasic acid to improve its fluidity. Examples of the aliphatic polybasic acid include saturated aliphatic dicarboxylic acids or their anhydrides, 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 their anhydrides, such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride; and trifunctional or more aliphatic carboxylic acids such as 1,2,3,4-butanetetracarboxylic acid.

[0063] The aforementioned polyester resin may be one that has been synthesized as appropriate, or a commercially available product may be used. Examples of such commercially available products include the Byronal series (manufactured by Toyobo Co., Ltd.), such as MD1335 and MD1480, and the Elitel series (manufactured by Unitika Ltd.), such as KT-0507, KT-8904, KT-8701, and KT-9204.

[0064] The total content of acrylic resin and polyester resin in 100% by mass of the resin contained in the adhesive ink is preferably 50% by mass or more, more preferably 80% by mass or more, 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 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 incorporated into the adhesive ink, it is preferable to add it as an emulsion; that is, in the adhesive ink of the present invention, it is preferable that the resin is included as emulsion particles.

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

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

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

[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 also, 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 to the above range, the effects of the present invention can be further enhanced while maintaining the viscosity of the adhesive ink within an appropriate range.

[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 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 mentioned above include those similar to those described as water-soluble organic solvents used in emulsion polymerization. The inclusion of a water-soluble organic solvent in the adhesive ink enhances its moisture retention and compatibility with the resin. The water-soluble organic solvent may be used alone or in combination of two or more types. The content of the water-soluble organic solvent is preferably 10 to 55 parts by mass, and 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 moisturizing properties, a water-soluble organic solvent with a boiling point of 150°C or higher is preferred, a water-soluble organic solvent with a boiling point of 180°C or higher is more preferred, and a water-soluble organic solvent with a boiling point of 200°C or higher is even more preferred. Examples of water-soluble organic solvents with 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 that further enhances moisturizing properties 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. Furthermore, from the viewpoint of further improving compatibility with the resin, a water-soluble organic solvent having a hydrophobic group (e.g., alkyl group) and a hydroxyl group is preferred, and at least one selected from the group consisting of monoalkyl ether of diethylene glycol, monoalkyl ether of dipropylene glycol, monoalkyl ether of polyethylene glycol (number of moles of EO added = 2 to 10), and monoalkyl ether of polypropylene glycol (number of moles of PO added = 2 to 10) is more preferred, and among these, at least one selected from the group consisting of diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, monobutyl ether of polyethylene glycol (number of moles of EO added = 2 to 4) (especially triethylene glycol monobutyl ether), and monomethyl ether of polypropylene glycol (number of moles of PO added = 2 to 10, preferably 2 to 4) (especially tripropylene glycol monomethyl ether) is even more preferred. The content of the water-soluble organic solvent that further improves compatibility is preferably 1 to 15 parts by mass, and 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 may be, for example, 70% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more, 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. It is believed that by using a crosslinking agent, a crosslinked structure can be formed through interaction with the components contained in the adhesive ink of the present invention, such as resins, or through chemical reactions, thereby forming a tough coating film. It is therefore presumed that the wet friction fastness and wash fastness (hereinafter sometimes collectively referred to as fastness) of the resulting printed material will be further improved.

[0075] Examples of the crosslinking agent include isocyanate compounds, epoxy compounds, melamine compounds, metal chelate compounds, aziridine compounds, mercapto compounds, and oxazoline compounds, with oxazoline compounds being preferred. The crosslinking agent may be used alone or in combination of two or more types.

[0076] The oxazoline compounds used as crosslinking agents mentioned above refer to compounds having two or more oxazoline groups in their molecule. Examples of the oxazoline compounds mentioned above 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), and 2,2'-ethylene-bis(4 Examples include, but are not limited to, 4'-dimethyl-2-oxazoline, 2,2'-p-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(4,4'-dimethyl-2-oxazoline), bis(2-oxazolinylcyclohexane) sulfide, bis(2-oxazolinylnorbornane) sulfide, and oxazoline group-containing polymers.

[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, one method can be used to polymerize one or more addition-polymerizable oxazolines, or a monomer component containing an addition-polymerizable oxazoline and a monomer copolymerizable with addition-polymerizable oxazolines. As copolymerizable monomers, monomers that do not have a functional group that reacts with an oxazoline group and are copolymerizable with an addition-polymerizable oxazoline are preferred. For example, monomers that do not have a functional group that reacts with an oxazoline group in the above monomer component can be mentioned. For example, (meth)acrylic monomers such as alkyl (meth)acrylates; styrene monomers such as styrene, α-methylstyrene, and chloromethylstyrene; vinyl monomers such as vinyl acetate, vinyl chloride, and vinyl benzoate; acrylonitrile; (meth)acrylamide monomers such as acrylamide; olefin monomers such as ethylene and propylene.

[0078] Examples of the above-mentioned addition-polymerizable oxazolines include compounds having a polymerizable unsaturated group and an oxazoline group in their 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 oxazoline group-containing polymers, water-soluble oxazoline group-containing polymers are preferred and can be produced by the same method as the above-mentioned method for producing oxazoline group-containing polymers. Examples of the above-mentioned water-soluble oxazoline group-containing polymers include polymers that have an acrylic resin or the like as the main chain and contain oxazoline groups in the side chains.

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

[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, per 100 parts by mass of the resin.

[0082] <Surfactants> The adhesive ink of the present invention may further contain a surfactant. By using a surfactant, it becomes possible to adjust the surface tension to one suitable for inkjet ejection.

[0083] As the surfactants mentioned above, it is preferable to use, for example, acetylene glycol-based surfactants, silicone-based surfactants, fluorine-based surfactants, etc. As the acetylene glycol-based surfactant, commercially available products may be used, specifically including the Surfinol series (manufactured by Evonik), the Orfin series (manufactured by Nisshin Chemical Industry Co., Ltd.), and the Acetyleneol series (manufactured by Kawaken Fine Chemical Co., Ltd.). As the silicone-based surfactant, a polyether-modified silicone-based surfactant is preferably used. Commercially available products may be used as the silicone-based surfactant, specifically the Silface series (manufactured by Nisshin Chemical Industry Co., Ltd.), the KF series (manufactured by Nisshin Chemical Industry Co., Ltd.), BYK-345, 347, 348, 349, 3450, 3451, 3455, and 3480 (all manufactured by BYK). Examples of the fluorinated surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains. Commercially available products may be used as the fluorinated surfactants, specifically the Surflon series (manufactured by AGC Seikamika Co., Ltd.) and the Megafac F series (manufactured by DIC Corporation). These surfactants may be used individually or in combination of two or more.

[0084] The surfactants mentioned above are preferably acetylene glycol-based surfactants and silicone-based surfactants, more preferably silicone-based surfactants, and even more preferably polyether-modified silicone-based surfactants.

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

[0086] Furthermore, using two or more of the above-mentioned surfactants is preferable because it makes it easier to adjust the surface tension to one 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, based on 100% by mass of the adhesive ink of the present invention.

[0087] In particular, it is preferable to use a silicone-based surfactant and an acetylene glycol-based surfactant in combination, and more preferably to use a polyether-modified silicone-based surfactant and an acetylene glycol-based surfactant in combination. Using these in combination improves the discharge stability of the adhesive ink.

[0088] When using a silicone-based surfactant and an acetylene glycol-based surfactant in combination, the mass ratio (silicone-based surfactant / acetylene glycol-based 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 (polyether-modified silicone-based surfactant / acetylene glycol-based surfactant) of the polyether-modified silicone-based surfactant to the acetylene glycol-based surfactant within the above range.

[0089] <Colorants> The adhesive ink of the present invention may further contain colorants such as dyes or pigments. The presence of colorants in the adhesive ink allows it to also function as a colored ink, as described later. Specifically, it becomes possible to form patterns such as desired images or characters using only the adhesive ink, or to form a white background layer that serves as the background for patterns formed from the colored ink layer. This reduces the number of colored ink prints or even eliminates the colored ink printing process altogether. However, from the viewpoint of achieving particularly excellent fastness of the resulting printed material, it is preferable that the adhesive ink of the present invention does not contain colorants.

[0090] As for the coloring material, it is preferable that it be a pigment from the viewpoint of fastness. Examples of pigments contained in adhesive inks are those exemplified as pigments contained in colored inks described later, and the preferred embodiments are the same.

[0091] The pigment content is, for example, 0 to 15% by mass or more per 100% by mass of the adhesive ink of the present invention. In particular, from the viewpoint of improving color development and design 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 meltability 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 per 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% by mass, and more preferably 1.5 to 7% by mass, of 100% by mass of the adhesive ink of the present invention, from the viewpoint of achieving both color development, design properties, hot meltability, and fastness. Furthermore, if the pigment is a coloring pigment, the content of the coloring pigment is preferably 1 to 5% by mass, and more preferably 1.5 to 3% by mass, of 100% by mass of the adhesive ink of the present invention, from the viewpoint of achieving both color development and design properties as well as hot meltability and durability.

[0092] <Other ingredients> The adhesive ink of the present invention may contain other components besides those described above, as long as the objectives of the present invention are not hindered. For example, appropriate amounts of additives such as dispersants, leveling agents, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, defoamers, antioxidants, crosslinking accelerators, pH adjusters, preservatives, chain transfer agents, and chelating agents may be included.

[0093] When adding the above-mentioned other components, 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 adhesive ink of the present invention. Furthermore, to exhibit the additive effect, it is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more.

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

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

[0096] From the viewpoint 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 that is, it is preferable to adjust the solid content of the emulsion to the above range. In this specification, non-volatile content (solid content) refers to the components excluding the solvent.

[0097] The solvent that serves 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 those described above. The solvent that serves as the dispersion medium for the emulsion particles may, for example, be derived from a solvent used in the production of the resin, or from a solvent separately added to the produced resin or a commercially available resin. Alternatively, a commercially available emulsion can be used.

[0098] When mixing a resin (preferably an emulsion), water, a water-soluble organic solvent, and, if necessary, a crosslinking agent, surfactant, colorant, and other components, the crosslinking agent, surfactant, colorant, and other additives may be used as is, or added as a solution diluted or dispersed with a solvent or the like. In particular, when using pigments as colorants, it is preferable to prepare a pigment dispersion in advance by mixing the pigment, dispersant, and solvent, and dispersing them using a bead mill or the like, so that the pigment is dispersed in the solvent, and then mix this with the other components. Examples of pigment dispersions used in the manufacture of adhesive inks are the same as those used in the manufacture of colored inks described later, and the preferred embodiments are also the same.

[0099] The method and order in which the above components are mixed are not particularly limited. After mixing, centrifugation or filtration can be performed as needed.

[0100] As described above, the adhesive ink of the present invention is an inkjet adhesive ink used for transfer printing onto fabrics. In other words, the present invention also includes a method of using the adhesive ink of the present invention as an adhesive ink for manufacturing a transfer medium used for transfer printing onto fabrics by an inkjet method. The adhesive ink used in the above method is as described above, and the preferred embodiment is the same. Furthermore, preferred embodiments of the transfer medium will be described in the section on transfer mediums below.

[0101] 2. Ink Set The present invention also includes an ink set comprising the aforementioned adhesive ink and a colored ink containing a pigment and a resin.

[0102] The adhesive ink constituting the ink set of the present invention is as described above, and the preferred embodiment is the same.

[0103] The hue of the colored ink 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 magenta, yellow, and cyan, which are the three primary colors of subtractive color mixing, as well as colors of different intensities such as light cyan, dark yellow, light magenta, and light black. Furthermore, one or more hues may be selected from red, blue, orange, green, and violet. In this specification, pigments that exhibit a white hue may be referred to as white pigments, and pigments that exhibit hues other than white (chromatic colors or black) may be referred to as colored pigments.

[0104] The hue of the colored ink can be controlled by the pigment. The pigment contained in the colored ink is not particularly limited, but pigments commonly used in inkjet printing colored inks can be used. Examples of such pigments include organic pigments and inorganic pigments, which may be used individually or in combination of two or more types. In addition, if necessary, they may be used in combination with extender pigments.

[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, isoindolinone pigments such as iminoisoindoline pigments and iminoisoindolinone, dioxazine pigments, quinacridone pigments such as quinacridone red and quinacridone violet, flavanthron pigments, indanthron pigments, anthrapyrimidine pigments, carbazole pigments, monoallylide yellow, diallylide yellow, benzimimidazolone yellow, toryl orange, naphthol orange, and quinophthalone pigments.

[0106] The hue of the organic pigment is not particularly limited, and any pigment exhibiting the aforementioned chromatic hues can be used. Specific examples of such organic pigments include product codes such as 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 oxide (such as zinc oxide), lithopone, lead white, red iron oxide, black iron oxide, chromium green oxide, carbon black, lead yellow, molybdenum red, ferric ferrocyanide (Prussian blue), ultramarine, and lead chromate. Other examples of inorganic pigments include flattened pigments such as mica, clay, aluminum powder, talc, and aluminum silicate, as well as extender pigments such as calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, and magnesium carbonate. Furthermore, examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black.

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

[0109] Preferred coloring pigments include the above-mentioned organic pigments, red iron oxide, black iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, ferric ferrocyanide (Prussian blue), ultramarine, and lead chromate.

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

[0111] The average particle size (volume-based) of pigments can be measured using a laser diffraction scattering particle size 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, if measurement by dynamic light scattering is difficult, such as with black pigments, the 50% particle size in the volume-based particle size distribution obtained by measuring with a laser diffraction scattering particle size analyzer can be used as the average particle size.

[0112] It is preferable that the pigment is dispersed and stabilized with a dispersant in the colored ink. For this reason, in the production of colored ink, it is preferable to prepare a pigment dispersion in which the pigment is dispersed in the solvent by mixing the pigment, dispersant, and solvent and performing a dispersion treatment with a bead mill or the like, and then mix this with a resin or any other component described later to produce colored ink.

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

[0114] As the solvent in the pigment dispersion, an aqueous solvent is preferred, and examples of aqueous solvents include those described as aqueous solvents used in emulsion polymerization.

[0115] The pigment content in the aforementioned colored 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 colored ink is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. Furthermore, when the pigment is an organic pigment, the content of the organic pigment in the colored ink is preferably 1 to 30% by mass, and more preferably 2 to 15% by mass.

[0116] The type of resin contained in the colored ink that constitutes the ink set of the present invention is not particularly limited, and examples include vinyl resins, acrylic resins, polyester resins, olefin resins, urethane resins, fluororesins, silicone resins, epoxy resins, phenoxy resins, phenolic resins, xylene resins, etc., among which 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 coloring ink is 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 polyester resin is used as the adhesive ink, it is preferable that an acrylic resin and / or polyester resin is also used as the resin used in the coloring ink, and it is even more preferable that when an acrylic resin is used as the adhesive ink, an acrylic resin is also used as the resin used in the coloring ink, or when a polyester resin is used as the adhesive ink, a polyester resin is also used as the resin used in the coloring ink. By using this ink set, the interface between the layer formed from the adhesive ink and the layer formed from the coloring ink in the transfer medium or printed material becomes less prone to peeling, and as a result, the transferability and the fastness of the resulting printed material are further improved.

[0118] Conventional acrylic resins can be used as the acrylic resin used in the colored ink. In particular, it is preferable that the resin contains structural units derived from (meth)acrylic monomers. Specific examples of (meth)acrylic monomers are the same as those described for (meth)acrylic monomers used in adhesive inks. 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 is C 1-18 Alkyl (meth)acrylates are preferred, C 4-12 Alkyl (meth)acrylates are more preferred. In particular, the alkyl (meth)acrylate is at least C 4-12 Preferably contains a linear alkyl acrylate, C 4-12 Chain-like alkyl acrylate and C 4-12 It is more preferable to include a cyclic alkyl methacrylate.

[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 100% by mass of the total 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 alkyl (meth)acrylate-derived structural units relative to 100% by mass of the total amount of structural units derived from all monomer components constituting the acrylic resin used in the colored ink 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 per 100 parts by mass of structural units derived from linear alkyl acrylates 4-12 The content of structural units derived from cyclic alkyl methacrylate is preferably 1 to 100 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 20 parts by mass. The content of structural units derived from (meth)acrylic acid (salt) relative to 100% by mass of the total structural units derived from all monomer components constituting the acrylic resin used in the colored ink 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 to the above range, the friction fastness and wash fastness of the resulting printed material can be further improved. The content of structural units derived from hydroxyalkyl (meth)acrylate, relative to 100% by mass of the total structural units derived from all monomer components constituting the acrylic resin used in the colored ink, 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 to the above range, the water resistance of the resulting printed material can be improved.

[0121] The acrylic resin used in the colored ink may further contain structural units derived from styrene monomers. The total content of structural units derived from (meth)acrylic monomers and styrene monomers, relative to 100% by mass of the total structural units derived from all monomer components constituting the acrylic resin used in the colored ink, is preferably 50% 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. Specific examples of the styrene monomer are the same as those described for styrene monomers used in adhesive inks. The content of structural units derived from styrene monomers relative to 100 parts by mass of 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 have 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 acid group-containing monomers used in adhesive inks (excluding (meth)acrylic acid) and the monomers described as other monomers.

[0123] Conventional polyester resins can be used as the polyester resin used in the colored ink. Preferably, the polyester resin is a condensation polymer of an aromatic dicarboxylic acid and a diol compound, and specific examples of the aromatic dicarboxylic acid and diol compound are the same as those described above.

[0124] The weight-average molecular weight (Mw) of the resin used in the colored ink is not particularly limited, but from the viewpoint of suppressing the flow of the colored 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 colored 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 coloring ink is not particularly limited, but from the viewpoint of further enhancing the texture of the resulting printed material, it is preferably -50 to 10°C, more preferably -45 to 5°C, and even more preferably -40 to 3°C.

[0126] When incorporating resin into colored ink, it is preferable to add it as an emulsion; that is, in colored ink, it is preferable that the resin be contained as emulsion particles. The preferred embodiments of the composition and physical properties of the resin constituting the emulsion particles are the same as described above.

[0127] The resin content (preferably emulsion particles) in the colored 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 resin content within the above range, the viscosity of the colored ink can be maintained within an appropriate range.

[0128] The colored ink preferably further contains a solvent. Suitable solvents include organic solvents and aqueous solvents, but from the viewpoint of reducing environmental impact, aqueous solvents are preferred. Examples of aqueous solvents include water and mixed solvents of water and water-soluble organic solvents. From the viewpoint of improving moisture retention and compatibility with resins, the aqueous solvent contained in the colored ink preferably includes a water-soluble organic solvent. The preferred type and content of the water-soluble organic solvent are the same as those for the water-soluble organic solvent in adhesive inks.

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

[0130] The colored ink may further contain a crosslinking agent. It is presumed that by using a crosslinking agent, a crosslinked structure can be formed through interaction with components contained in the colored ink, such as resins, or through chemical reactions, thereby forming a tough coating film, and thus the wet friction fastness and wash fastness of the resulting printed material will be further improved. Examples of crosslinking agents that can be used in colored inks include the compounds exemplified as crosslinking agents that can be used in adhesive inks, and the preferred embodiments thereof are similar.

[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, per 100 parts by mass of the resin.

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

[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, based on 100% by mass of the colored ink.

[0134] The colored ink may contain other components besides those described above, as long as the objectives of the present invention are not hindered. For example, it may contain appropriate amounts of additives such as leveling agents, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, defoamers, dyes, antioxidants, crosslinking accelerators, pH adjusters, and preservatives. When adding the above-mentioned other components, their content is not particularly limited, but is preferably 2% by mass or less, and more preferably 1% by mass or less, based on 100% by mass of the colored ink. Furthermore, to exhibit the additive effect, it 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 includes transfer media on which the adhesive ink of the present invention is printed on a transfer substrate, either via or without a colored ink layer formed from a colored ink containing a pigment and a resin. The transfer media of the present invention is formed using the aforementioned adhesive ink, and therefore, by using this transfer medium, excellent transferability during transfer printing to fabrics can be achieved, and the wet friction fastness and texture of the resulting printed material can be improved. In particular, as a transfer medium on which the adhesive ink is printed on a transfer substrate via a colored ink layer, it is preferable that the transfer substrate is printed with a colored ink containing a pigment and a resin, and the adhesive ink of the present invention is further printed on the colored ink. Hereinafter, the layer formed by printing colored ink, i.e., the layer formed from colored ink, may be referred to as the colored ink layer, and the layer formed by printing adhesive ink, i.e., the layer formed from adhesive ink, may be referred to as the adhesive ink layer. In the transfer medium of the present invention, the colored ink layer and the adhesive ink layer are formed to be peelable from the transfer substrate.

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

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

[0138] Figure 1 is a schematic cross-sectional view showing an example of the layered structure of the transfer medium of the present invention. Figures 1(a) and 1(b) show examples of transfer medium A. In (a) and 1(b), the transfer medium 100 has a colored ink layer 2 on a transfer substrate 1, and an adhesive ink layer 3 is further provided on the colored ink layer 2. The adhesive ink layer 3 may be provided only in the portion where the colored ink layer 2 is formed, as shown in Figure 1(a), or it may be provided not only in the portion where the colored ink layer 2 is formed but also around it, as shown in Figure 1(b). The embodiment shown in (b) is preferable because it further improves the wet friction fastness of the resulting printed material. Figure 1(c) shows an example of transfer medium B. In the transfer medium 100 in (c), the adhesive ink layer 3 is directly laminated on the transfer substrate 1. The form of transfer medium B (for example, the form shown in Figure 1(c)) is particularly preferable when the adhesive ink forming the adhesive ink layer 3 contains a colorant.

[0139] The transfer substrate is not particularly limited, but a material that does not shrink easily during the drying process described later is preferred. Specific examples of transfer substrates include metal, wood, plastic, or paper. Examples of the aforementioned metals include aluminum and copper, with aluminum being preferred from a cost standpoint. Examples of the aforementioned plastics include polyolefin resins, polyester resins, polyamide resins, and polycarbonate resins. From a cost standpoint, polyester resins are preferred, and aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate are more preferred. Examples of the above-mentioned papers include plain paper, fine paper, and coated paper.

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

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

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

[0143] In the present invention, it is preferable that the transfer medium has an ink receiving layer on the surface of the transfer substrate on which the colored ink and / or adhesive ink are printed. Specifically, in transfer medium A, it is preferable that an ink receiving layer is provided between the transfer substrate and the colored ink layer, and in transfer medium B, it is preferable that an ink receiving layer is provided between the transfer substrate and the adhesive ink layer. By providing an ink receiving layer, it is possible to suppress the flow or collapse of the colored ink or adhesive ink printed on the ink receiving layer, and the durability of the colored ink layer or adhesive ink layer after it has been transferred to the fabric can be further improved.

[0144] Figure 2 is a schematic cross-sectional view showing an example of the laminated 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 using the form of transfer medium B, the transfer medium 100 may be provided with an ink receiving layer 4 on a transfer substrate 1, and an adhesive ink layer 3 laminated 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 later) with a solution containing an ink-receiving layer-forming resin. Examples of the resin include (meth)acrylic resins such as (meth)acrylic acid ester resins and (meth)acrylic acid ester-styrene copolymer resins; olefin resins such as polyethylene resins and polypropylene resins; silicone resins; polyvinyl alcohol resins; cellulose resins such as sodium carboxymethylcellulose; and the like. The solution containing the ink-receiving layer-forming resin may further contain inorganic particles such as calcium carbonate and silica.

[0146] The thickness of the ink receiving layer is not particularly limited, but from the viewpoint of suppressing the flow of colored ink and adhesive ink, it is preferably 30 nm or more, and more preferably 100 nm or more. Also from the viewpoint of cost, it is preferably 20 μm or less, and more preferably 10 μm or less. In other words, the thickness of the ink receiving layer is preferably 30 nm to 20 μm, and more preferably 100 nm to 10 μm.

[0147] Furthermore, the transfer medium of the present invention may have a release layer provided on at least one surface of the transfer substrate. That is, in transfer medium A, a release layer may be provided between the transfer substrate and the colored ink layer (preferably the ink receiving layer) and / or on the side of the transfer substrate opposite to the surface on which the colored ink layer is formed. Similarly, in transfer medium B, a release layer may be provided between the transfer substrate and the adhesive ink layer (preferably the ink receiving layer) and / or on the side of the transfer substrate opposite to the surface 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 substrate and the colored ink layer or adhesive ink layer to be transferred are made easier to separate, thus making transfer from the transfer medium to the fabric easier. In addition, by providing a release layer on the side of the transfer medium opposite to the surface on which the colored ink layer or adhesive ink layer is formed, blocking between transfer mediums can be suppressed when the transfer mediums are stacked.

[0148] Figure 3 is a schematic cross-sectional view showing an example of a laminated structure of a transfer medium A having an ink receiving layer and a release layer. In Figure 3(d), the transfer medium 100 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. In Figure 3(e), the transfer medium 100 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. In Figure 3(f), the transfer medium 100 has release layers 5 on both sides of the transfer substrate 1, an ink receiving layer 4 on one of the release layers 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 using the form of transfer medium B, the transfer medium 100 can be made in which the adhesive ink layer 3 is directly laminated on the ink receiving layer 4, as shown in Figures 3(d) to (f).

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

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

[0151] Sheets and films having an ink-receiving layer and / or a release layer on a transfer substrate are commercially available, and a transfer medium may be constructed using such commercially available products. An example of such a commercially available product is DTF Transfers film (manufactured by One More Buck).

[0152] In the transfer medium of the present invention, the colored ink that forms the colored ink layer is the same as the colored ink that constitutes the ink set described above, and the preferred embodiment is also the same.

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

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

[0155] The discharge weight per unit area of ​​the colored ink in the transfer medium of the present invention is not particularly limited, but is generally between 1 and 200 g / m². 2 Preferably, 5-100 g / m 2 This is even more preferable. Forming a colored ink layer within this range tends to result in a printed product with even better texture and wet abrasion fastness.

[0156] In the transfer medium of the present invention, the adhesive ink that forms the adhesive ink layer is the same as that described above as the adhesive ink, and the preferred embodiment thereof is 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 greater than 5 μm, and particularly preferably 8 μm or more, as of the film thickness after drying. By adjusting the adhesive ink to the above thickness, the transferability and wet friction fastness of the resulting printed material are improved. Furthermore, from the viewpoint of improving the texture of the resulting printed material, 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 also be 50 μm or less. In other words, 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 also be 8 to 50 μm.

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

[0159] If step 3 is a step of printing adhesive ink onto a colored ink layer laminated on a transfer substrate using an inkjet printer, it is preferable that the colored ink layer is formed by step 1 of printing colored ink onto the transfer substrate using an inkjet printer and step 2 of drying the colored ink. The following details each step.

[0160] [Process 1] Step 1 is the process of printing colored ink onto a transfer substrate using an inkjet printer. An example of an apparatus for performing Step 1 is an inkjet recording device, and a specific example of an inkjet recording device is the MMP-TX13 (manufactured by Mastermind Corporation), although it is not limited to the following. When using an inkjet recording device, colored ink can be printed onto the transfer substrate by ejecting colored ink from an inkjet head and adhering the colored ink to a predetermined portion on the transfer substrate. This forms a pattern of colored ink layers on the transfer substrate. Note that "printing colored ink onto a transfer substrate using an inkjet printer" includes not only the method of directly printing colored ink onto the transfer substrate using an inkjet printer, but also the method of printing colored ink onto a laminate in which other layers such as an ink-receiving layer and / or a release layer are provided on the transfer substrate using an inkjet printer.

[0161] The colored ink used in step 1 is the same as the colored ink that constitutes the ink set described above, and its preferred embodiment is also the same.

[0162] The number of times the colored ink is printed is not particularly limited, for example, 1 to 6 times, preferably 1 to 4 times. When printing multiple times, the colored ink used in each print may be the same or different. For example, after printing with a colored ink to form a pattern such as the desired image or text, printing may be done again with a white colored ink. By going through this printing process, a white base layer is formed between the fabric and the pattern in the resulting printed material, resulting in good color development, especially when using dark-colored fabrics. Note that when forming the white base layer between the fabric and the pattern, if an adhesive ink containing a white pigment is used in step 3 described later, the printing step of the white colored ink can be omitted.

[0163] In step 1, the amount of ink ejected in a single print is not particularly limited and can be determined according to the desired thickness of the colored ink layer, but it can be adjusted within the range of, for example, 3 to 15 ng.

[0164] [Process 2] Step 2 is a step of drying the colored ink printed on the transfer substrate. In other words, step 2 is a step of evaporating some or all of the components (i.e., solvents) of the colored ink printed on the transfer substrate, excluding the solid components. Even if an ink receiving layer is provided on the printing surface of the transfer substrate, when adhesive ink is printed on top of it, the colored ink may flow, making it difficult to obtain a clear pattern. Therefore, it is preferable to go through drying step 2.

[0165] In step 2, of the 100% by mass of the components of the colored 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 amount of evaporation to the above range, the flow of the adhesive ink in step 3, described later, can be suppressed. Also, in step 2, of the 100% by mass of the components of the colored 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 amount of evaporation to the above range, the colored ink layer and the adhesive ink layer mix appropriately at the interface between them, and peeling at the interface during transfer printing can be suppressed, thus improving transferability. In other words, the amount of evaporation 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. Furthermore, by using a colored ink with a known solid content concentration, dispensing a certain weight of the colored ink onto the substrate, and then measuring the total weight of the ink and substrate, as well as the weight of the substrate alone, using a precision balance, the conditions for the desired evaporation rate can be determined. The drying process in step 2 can then be performed under the same conditions.

[0166] The apparatus for carrying out step 2 is not particularly limited, but for example, heating means in an inkjet recording device (e.g., platen heater, hot air heater, infrared heater) can be used. Among these, a platen heater is preferred 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 amount of evaporation described above can be adjusted by controlling the heating temperature, heating time, hot air temperature, and airflow rate. It is preferable to set the conditions for the heater in advance by measuring the amount of evaporation before the experiment. For example, when using a platen heater or a planar heating element as an alternative, the colored ink can be dried by heating the back surface 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, and more preferably 40°C or higher. Also, if the heating temperature of the platen heater or planar heating element is too high, heat may be transferred to the inkjet head, potentially causing nozzle blockage, so it is preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 60°C or lower. In other words, 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, it may be performed continuously from the start to the end of Step 1, or intermittently, but continuous performance is preferred. For example, when printing colored ink multiple times, it is preferable to dry the colored ink during and / or after the printing of each colored ink. In this case, the amount of evaporation of the components excluding solids in each colored ink may be adjusted to the above range, or the amount of evaporation of the components excluding solids in all colored inks may be adjusted to the above range.

[0169] By going through steps 1 and 2, a colored ink layer can be laminated onto the transfer substrate. The colored ink layer forms the pattern of the desired image or characters. However, if the adhesive ink used in step 3, described later, contains a colorant, the desired pattern can be formed using the adhesive ink, and steps 1 and 2 can be omitted.

[0170] [Process 3] Step 3 is the process of printing adhesive ink onto a transfer substrate or onto a colored ink layer laminated on a transfer substrate using an inkjet printer. The "process of printing adhesive ink onto a transfer substrate using an inkjet printer" includes not only the method of directly printing adhesive ink onto the transfer substrate using an inkjet printer, but also the method of printing adhesive ink onto a laminate that has other layers such as an ink-receiving layer and / or a release layer (excluding the colored ink layer) on the transfer substrate using an inkjet printer. For example, when producing a transfer medium A having an ink-receiving layer, it is preferable that the printing of the adhesive ink in step 3 is performed on the side of the colored ink layer in a laminate where the transfer substrate, ink-receiving layer, and colored ink layer are laminated in that order. Similarly, when producing a transfer medium B having an ink-receiving layer, it is preferable that the printing of the adhesive ink in step 3 is performed on the ink-receiving layer laminated on the transfer substrate.

[0171] The adhesive ink used in step 3 is the same as the adhesive ink described above, and its preferred embodiment is also the same.

[0172] An inkjet recording device similar to that used in step 1 can be used as the apparatus for carrying out step 3. When using an inkjet recording device, adhesive ink is ejected from the inkjet head and the adhesive ink can be printed by adhering the adhesive ink onto the transfer substrate or the ink receiving layer and / or release layer provided on the transfer substrate, or onto the colored ink layer formed in step 2. As a result, an adhesive ink layer is formed on the transfer substrate or the ink receiving layer and / or release layer provided on the transfer substrate, or on the colored ink layer. When printing (adhering) the adhesive ink onto the colored ink layer, a transfer medium as shown in Figure 1(b) can be obtained by printing (adhering) not only onto the colored ink layer but also around it.

[0173] By using an inkjet recording device equipped with multiple inkjet heads, it is possible to continuously print with colored ink and adhesive ink. For example, by installing the aforementioned ink sets, which include one or more types of colored ink and adhesive ink, into each ink cartridge of the inkjet recording device, and ejecting ink from each inkjet head corresponding to each ink cartridge, it is possible to continuously print with colored ink and adhesive ink.

[0174] The number of times the adhesive ink is printed is not particularly limited and can be determined according to the desired thickness of the adhesive ink layer, but for example, it is 1 to 6 times, preferably 1 to 4 times. Also, in step 3, the amount of ink ejected in one print is not particularly limited and can be determined according to the desired thickness of the adhesive ink layer, but for example, it can be adjusted in the range of 3 to 15 ng.

[0175] [Step 4] Step 4 is the process of drying the adhesive ink printed on the transfer substrate or colored ink. In other words, step 4 is the process of evaporating some or all of the components (i.e., the solvent) of the colored ink or adhesive ink printed in steps 1 and 3, excluding the solid components.

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

[0177] The apparatus for carrying out step 4 is not particularly limited, but for example, heating means in an inkjet recording device (e.g., platen heater, hot air heater, infrared heater, etc.) or planar heating elements such as rubber heaters installed on the platen and used as an alternative to the platen heater can be used. The amount of evaporation described above can be adjusted by controlling the heating temperature, heating time, hot air temperature, and airflow. It is preferable to set the conditions for the heater in advance by measuring the amount of evaporation before the experiment. For example, when using a platen heater or a planar heating element as an alternative, the colored ink and adhesive ink can be dried by heating the back surface 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. Also, if the heating temperature of the platen heater is too high, heat may be transferred to the inkjet head and cause nozzle blockage, so it is preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 60°C or lower. In other words, 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.

[0178] Furthermore, it is also preferable to dry the transfer medium after step 3 or after heating by the heating means or alternative means in the inkjet recording apparatus using means such as natural drying, heating, reduced pressure, and contact with dry air or hot air. In the means described above, the heating temperature, heating time, pressure, hot air temperature, and airflow rate can be appropriately set according to the desired amount of evaporation. 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, and 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 intermittently. In particular, it is preferable to continuously dry the adhesive ink using a heating means in the inkjet recording device during Step 3, and further dry it by heating or contact with hot air after Step 3. Also, when printing adhesive ink multiple times, it is preferable to dry the adhesive ink using a heating means or an alternative means in the inkjet recording device during and / or after the completion of printing each adhesive ink, and then dry it by heating or contact with hot air after all printing is completed. In that case, the amount of evaporation of the components excluding solids in each adhesive ink may be adjusted to the above range, or the amount of evaporation of the components excluding solids in all adhesive inks may be adjusted to the above range.

[0180] 4. Printed materials Printed textiles that have been transfer-printed using the adhesive ink described above, that is, printed textiles that have been transfer-printed using the transfer medium described above, are also included in the present invention. Because the printed textiles of the present invention use a specific adhesive ink, they have excellent wet friction fastness and texture. The method for manufacturing the printed textiles of the present invention will be described in detail below.

[0181] <Method of manufacturing printed materials> The printed material of the present invention is obtained by transferring the above-described transfer medium onto a fabric. The transfer medium used in the production of the printed material of the present invention is the same as that described above as a transfer medium, and its preferred embodiment is also the same.

[0182] The fabrics used are not particularly limited and encompass all textile products such as cloths and woven fabrics made from natural and / or synthetic fibers. Examples of fabrics include woven fabrics, nonwoven fabrics, knitted fabrics, etc. The fibers that make up the fabrics are also not particularly limited and include natural fibers, chemical fibers, or mixtures thereof.

[0183] Preferred natural fibers include, for example, silk, cotton, and wool. Chemical fibers include synthetic fibers, regenerated fibers, and semi-synthetic fibers. Preferred synthetic fibers include, for example, polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, polyethylene fibers, polypropylene fibers, and vinylon fibers. A preferred regenerated fiber is, for example, rayon. Preferred semi-synthetic fibers include acetate and triacetate. Among these, fabrics formed from cotton, polyester fibers, polypropylene fibers, nylon fibers, or mixtures thereof are preferred.

[0184] The transfer printing method is not particularly limited, and conventionally known methods can be used. For example, the transfer printing method preferably includes the steps of bringing the side of the transfer medium on which the adhesive ink layer is formed (i.e., the adhesive ink printed side) into close contact with the fabric, and peeling the transfer substrate from the fabric. This makes it possible to peel off the transfer substrate while leaving the printed adhesive ink (adhesive ink layer) on the fabric side.

[0185] Figure 4 is a schematic cross-sectional view showing an example of the laminated structure of transfer medium A and fabric in the adhesion process. The surface of the transfer medium 100 on which the adhesive ink layer 3 is formed is positioned opposite the fabric 6 and they are in close contact. Preferably, a portion of the adhesive ink layer 3 is embedded in the fabric 6. This further improves the wet friction fastness of the resulting printed material. The same applies when using transfer medium B.

[0186] The above adhesion process preferably includes heating and pressurizing, if necessary. The adhesion process can be, for example, a method of adhering the transfer medium to the fabric using a press or a heated drum, followed by heating and pressurizing.

[0187] The heating temperature in the adhesion process is not particularly limited, but is preferably 80 to 200°C, and more preferably 100 to 180°C. The pressure during the adhesion process is not particularly limited, but is generally between 100 and 600 g / cm². 2 Preferably, it is 200-500 g / cm³. 2 That is the case.

[0188] From the viewpoint of further improving transferability, the contact time is preferably 1 second or more, and more preferably 3 seconds or more. While there is no particular upper limit to the contact time, from the viewpoint of productivity, it is preferably 1 minute or less, and more preferably 30 seconds or less. In other words, the contact time is preferably 1 second to 1 minute, and more preferably 3 seconds to 30 seconds.

[0189] After the adhesion process, the printed material is obtained by peeling the transfer substrate off the fabric. It is preferable to peel off the transfer substrate after the fabric temperature has dropped to 60°C or below (especially 40°C or below) to reduce ink residue on the transfer substrate.

[0190] Furthermore, the resulting printed material may be heated and pressurized using a press or heated drum. By additionally heating and pressurizing the resulting printed material, the ink is more firmly bonded to the fabric, and the wet friction fastness is further improved. The heating temperature in this process is not particularly limited, but is preferably 80 to 200°C, and more preferably 100 to 180°C. The pressure in this process is not particularly limited, but is generally between 100 and 600 g / cm². 2 Preferably, it is 200-500 g / cm³. 2 That is the case. The heating and pressurizing time in this process 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 on 20 February 2023, and Japanese Patent Application No. 2023-027251, filed on 24 February 2023. The entire contents of the specification of Japanese Patent Application No. 2023-024440, filed on 20 February 2023, and the entire contents of the specification of Japanese Patent Application No. 2023-027251, filed on 24 February 2023, are incorporated herein by reference. [Examples]

[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 "percent mass".

[0193] [Ink adjustment]

[0194] (Emulsion manufacturing example 1) 280 parts of deionized water were charged into a polymerization reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube, and dropping funnel. The internal temperature was then raised to 75°C while stirring under a nitrogen gas stream. Meanwhile, a monomer emulsion consisting of 490 parts of methyl methacrylate, 490 parts of butyl acrylate, and 20 parts of acrylic acid, all monomer components; 4.0 parts of t-dodecyl mercaptan, 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), both emulsifiers that had been pre-prepared as 20% aqueous solutions, and 183.0 parts of deionized water was charged into the dropping funnel. Next, while maintaining the internal temperature of the polymerizer at 75°C, 27.0 parts of the monomer emulsion, 5 parts of a 5% potassium persulfate aqueous solution and 10 parts of a 2% sodium bisulfite aqueous solution, which are polymerization initiators (oxidizing agents), were added to start the initial polymerization. After 40 minutes, while maintaining the reaction system temperature at 80°C, the remaining monomer emulsion was uniformly added dropwise over 210 minutes. Simultaneously, 95 parts of a 5% potassium persulfate aqueous solution and 90 parts of a 2% sodium bisulfite aqueous solution were uniformly added dropwise over 210 minutes. After the addition was complete, the same temperature was maintained for 60 minutes to complete the polymerization. After cooling the resulting reaction solution to room temperature, 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). Emulsion 1 had a solid content of 55%, a Tg of 10°C for the emulsion particles contained in Emulsion 1, an average particle diameter of 200 nm, and a weight-average molecular weight of 300,000.

[0195] (Emulsion manufacturing example 2) Except for replacing 62.5 parts of Latemul WX, which was prepared as a 20% aqueous solution, with 62.5 parts of Adekaryasorb SR-10 (trade name, manufactured by ADEKA Corporation), which was prepared as a 20% aqueous solution, the reaction was carried out in the same manner as in Emulsion Production Example 1 to obtain an acrylic resin emulsion (hereinafter referred to as Emulsion 2). The solid content of Emulsion 2 was 55%, 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 manufacturing example 3) Except for using 20 parts of t-dodecyl mercaptan, the reaction was carried out in the same manner as in Emulsion Preparation Example 1 to obtain an acrylic resin emulsion (hereinafter referred to as Emulsion 3). Emulsion 3 had a solid content of 55%, a Tg of 3°C for the emulsion particles contained in Emulsion 3, an average particle diameter of 200 nm, and a weight-average molecular weight of 70,000.

[0197] (Emulsion manufacturing example 4) An acrylic resin emulsion (hereinafter referred to as emulsion 4) was obtained by carrying out the reaction in the same manner as in emulsion production example 1, except that the monomer components used were changed to 250 parts butyl acrylate, 490 parts styrene, 240 parts 2-ethylhexyl acrylate, and 20 parts acrylic acid. The solid content of emulsion 4 was 55%, 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 manufacturing example 5) Unitika's Elitel KT-0507 (polyester resin emulsion) (hereinafter referred to as Emulsion 5) was prepared. Emulsion 5 had a solid content of 25%, a Tg of the emulsion particles contained in Emulsion 5 at -21°C, an average particle diameter of 150 nm, and a weight-average molecular weight of 55,000.

[0199] (Emulsion manufacturing example 6) Unitika's Elitel KT-9204 (polyester resin emulsion) (hereinafter referred to as Emulsion 6) was prepared. Emulsion 6 had a solid content of 30%, a Tg of 22°C for the emulsion particles contained in Emulsion 6, an average particle diameter of 150 nm, and a weight-average molecular weight of 70,000.

[0200] (Emulsion manufacturing example 7) 252 parts of deionized water were placed in a flask equipped with a dropping funnel, stirrer, nitrogen gas inlet tube, thermometer, and reflux condenser. A dropper pre-emulsion was prepared in the dropping funnel, consisting of 437 parts of deionized water, 80 parts of a 25% aqueous solution of emulsifier (ADEKA Corporation, product name: Adekaryasorb SR-10), 25 parts of acrylic acid, 565 parts of 2-ethylhexyl acrylate, 50 parts of cyclohexyl methacrylate, 10 parts of hydroxyethyl methacrylate, and 350 parts of styrene. 44 parts of this dropper pre-emulsion, representing 3% of the total volume, were added to the flask, and the temperature was raised to 80°C while slowly blowing in nitrogen gas. 30 parts of a 5% aqueous solution of ammonium persulfate were added to initiate polymerization. Subsequently, the remaining dropper pre-emulsion and 30 parts of the 5% aqueous solution of ammonium persulfate were uniformly added dropwise to the flask over a period of 240 minutes. After the dropwise addition was complete, the contents of the flask were maintained at 80°C for 180 minutes, and the pH was adjusted to 8.5 and the solid content to 50% by adding 25% aqueous ammonia and deionized water, thereby terminating polymerization. After the resulting reaction solution was cooled to room temperature, an acrylic resin emulsion (hereinafter referred to as emulsion 7) was obtained by filtering through a 300-mesh wire mesh. Emulsion 7 had a solid content of 50%, a Tg of emulsion particles contained in emulsion 7 at -21°C, an average particle size of 200 nm, and a weight-average molecular weight of 1,100,000.

[0201] (Emulsion manufacturing example 8) Unitika's Elitel KT-8803 (polyester resin emulsion) (hereinafter referred to as Emulsion 8) was prepared. Emulsion 8 had a solid content of 30%, a Tg of 66°C for the emulsion particles contained in Emulsion 8, an average particle diameter of 100 nm, and a weight-average molecular weight of 50,000.

[0202] (Emulsion manufacturing example 9) Except for using 60 parts of t-dodecyl mercaptan, the reaction was carried out in the same manner as in Emulsion Preparation Example 1 to obtain an acrylic resin emulsion (hereinafter referred to as emulsion 9). Emulsion 9 had a solid content of 55%, a Tg of 2°C for the emulsion particles contained in emulsion 9, an average particle diameter of 200 nm, and a weight-average molecular weight of 7,000.

[0203] (Emulsion manufacturing example 10) An acrylic resin emulsion (hereinafter referred to as emulsion 10) was obtained by carrying out the reaction in the same manner as in emulsion production example 1, except that the monomer components used were changed to 498 parts methyl methacrylate, 498 parts butyl acrylate, and 4 parts acrylic acid. The solid content of emulsion 10 was 50%, 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 manufacturing example 11) An acrylic resin emulsion (hereinafter referred to as emulsion 11) was obtained by carrying out the reaction in the same manner as in emulsion production example 1, except that the monomer components used were changed to 500 parts methyl methacrylate and 500 parts butyl acrylate. The solid content of emulsion 11 was 50%, the Tg of the emulsion particles contained in emulsion 11 was 10°C, the average particle size was 200 nm, and the weight-average molecular weight was 300,000.

[0205] The measurement methods for each emulsion particle in the above production examples 1 to 11, such as Tg, average particle diameter, and weight-average molecular weight, 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: Airtight aluminum container Sample weight: 10 mg ± 2 mg Measurement method: Two cycles of heating from -50°C to 150°C were performed under an N2 atmosphere. The heating / cooling rate was 10°C / min, and the holding time at -50°C and 150°C was 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 value of the midpoint glass transition temperature was adopted.

[0207] (Measurement of the average particle size of emulsion particles) The average particle size (volume-based) of the emulsion particles was measured using a dynamic light scattering particle size distribution analyzer (Otsuka Electronics Co., Ltd., model number: FPAR-1000) with the emulsion obtained in each production example as the measurement sample, and 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 instrument: HLC-8320GPC (product name, manufactured by Tosoh Corporation) Molecular weight column: TSK-GEL SuperMultiporeHZ (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran (THF) Calibration standard material: Polystyrene (manufactured by Tosoh Corporation) Measurement method: The substance to be measured was dissolved in THF to a solid content of approximately 0.2% by mass, filtered, and the molecular weight was measured using the resulting sample. The liquid delivery pump flow rate was set to 0.35 ml / min.

[0209] (Example of Pigment Dispersion Production 1) Five parts of the dispersant Discoat N-14 (manufactured by Daiichi Kogyo Seiyaku), six parts of propylene glycol, seventy parts of deionized water, and 100 parts of titanium dioxide CR-95 (manufactured by Ishihara Sangyo) were packed into a mixture containing 50% volume of zirconia beads with a particle size of 0.5 mm. The mixture was dispersed using a bead mill and filtered through a 1 μm pore size filter (manufactured by Advantec, MCP-1-C10S) to obtain a white pigment dispersion containing 55% pigment (hereinafter referred to as pigment dispersion 1). The average particle size of the pigment was 330 nm.

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

[0211] (Measurement of average particle size of pigments) The average particle size (volume basis) of the aforementioned pigments was measured using a dynamic light scattering particle size distribution analyzer (manufactured by Otsuka Electronics Co., Ltd., model number: FPAR-1000) with the pigment dispersions obtained in each manufacturing example as measurement samples, and determined using cumulant analysis.

[0212] (Preparation of white ink) 30 parts of Emulsion 7 (15 parts as emulsion particles), 23 parts of Pigment Dispersion 1, 1.2 parts of Epocros WS-700 (manufactured by Nippon Shokubai Co., Ltd., solid content 25%) (0.3 parts as solid content), 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 were mixed and filtered through a 1-μm pore size filter (manufactured by Advantec, MCP-1-C10S) to produce white ink.

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

[0214] (Preparation of Adhesive Ink 1) 25 parts of Emulsion 1 as emulsion particles, 2 parts of diethylene glycol monobutyl ether, 15 parts of triethylene glycol, 0.6 parts of surfactant KF-6011 (manufactured by Shin-Etsu Chemical Co., Ltd.), and 36.9 parts of deionized water, a total of 100 parts were mixed and filtered through a 1-μm pore size filter (manufactured by 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, except that the types and amounts of each raw material in the preparation of Adhesive Ink 1 were changed as shown in Table 1, and the amount of deionized water was adjusted so that the total amount was 100 parts. Note that "Surfynol 440" in Table 1 indicates the trade name of an acetylene glycol-based surfactant manufactured by Evonik.

[0216]

Table 1

[0217] [Printing Device and Transfer Substrate] (Inkjet Printing Device) Two Mastermind printers (MMP-TX13) were prepared and designated as Printer A and Printer B. A rubber heater was placed on top of the platen of each printer and heated to 50°C. Printer A was filled with cyan and white inks. Printer B was filled with adhesive ink and cyan ink.

[0218] [Examples 1-22, Comparative Examples 1-5] Using the inks prepared above, the following printing and transfer processes were performed, and various characteristics were evaluated. The results are shown in Tables 2-4.

[0219] (Printing process) The transfer substrate was placed on a rubber heater, and the image was formed using an inkjet method. When using white ink, a solid print (8 x 16 cm) was made using cyan ink with printer A. 2 After doing that, a solid print (8 x 16 cm) of white ink is applied on top of it. 2 The printed transfer substrate was then transferred to printer B, and a solid print (8 x 16 cm) was made on top of it using adhesive ink. 2 ) was performed. If white ink is not used, solid print (8 x 16 cm) is done using cyan ink with printer B. 2 After doing that, solid print (8 x 16 cm) is applied on top with adhesive ink. 2 The following was performed: The amount of colored ink dispensed was 70 g / m² per unit area. 2 The transfer substrate used was a PET film with an ink-receiving layer on one side, and image formation was performed on the ink-receiving layer side.

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

[0221] (Transfer process) -Transfer process in Examples 1-20 and Comparative Examples 1-3- A Horizon International TP-630M transfer press was used. The heating temperature was 150°C, and the press load was 3kN (transfer pressure: 400g / cm²). 2 ) was set to this. The fabric to be transferred was placed on the lower pressing iron, and the transfer medium was then placed on top of it with the print side facing down, and stamped for 10 seconds. After stamping, once the temperature of the fabric had dropped to below 40°C, the transfer material was peeled off the fabric to obtain the printed image. The obtained printed image was then placed on the lower pressing iron again, silicone release paper was placed on top of the printed image, and stamped for 5 seconds to press the image onto the fabric. -Transfer process in Examples 21-22 and Comparative Examples 4-5- A Horizon International TP-630M transfer press was used. The heating temperature was 150°C, and the press load was 3kN (transfer pressure: 400g / cm²). 2 ) was set to this. The fabric to be transferred was placed on the lower pressing iron, and the transfer medium was then placed on top of it with the printing side facing down, and stamped for 3 seconds. After stamping, once the temperature of the fabric had dropped to below 40°C, the transfer material was peeled off the fabric to obtain the printed material.

[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-colored jacket manufactured by CAB Corporation (product number: 7059-01) was used as the nylon fabric.

[0223] [Characteristic evaluation] (1) Evaluation of transcriptional properties In each example and comparative example, the transfer substrate obtained after the transfer treatment was evaluated as follows: those with the image printed by the inkjet printer remaining were marked with ×, and those without the image remaining were marked with ○.

[0224] (2) Evaluation of the texture of the printed material Each printed material obtained in each example and comparative example was evaluated by touch. Materials that felt stiff were marked with ×, and materials that bent easily and had a softness close to that of the fabric itself were marked with ○. In comparative examples 1, 4, and 5, it was not possible to transfer all the inks, so the texture of the printed materials could not be evaluated.

[0225] (3) Evaluation of wet abrasion fastness of printed materials The printed materials obtained in each example and comparative example were subjected to a wet friction test using a Type II testing machine with attached white cloth made of cotton No. 3-1, under a load of 200g for 100 back-and-forth cycles, according to the method specified in JIS L0849, and evaluated using a grayscale of color change. In comparative examples 1, 4, and 5, it was not possible to transfer all of the inks, and therefore the wet friction fastness of the printed materials could not be evaluated. ◎: Wet friction test, contamination level 4-5 or higher. ○: Wet friction test, contamination level 3-4, or level 4 △: Wet friction test, contamination level 2-3, or level 3 ×: Wet friction test, contamination level 2 or lower.

[0226] (4) Evaluation of wash fastness of printed materials For each example and comparative example, the printed materials were washed by repeating the "wash → rinse → spin-dry" cycle five times consecutively under the following conditions, and the materials obtained after the fifth spin-drying cycle were used as samples. • Washing machine: Model number NA-F5B1 (manufactured by Panasonic) ·Water volume: 32L • Course: Select 1 rinse • Detergent: Ariel Liquid Laundry Detergent with Disinfectant (manufactured by P&G), amount to use: 35g For the samples obtained by the above method, the washing fastness was evaluated from the exposure rate of the fabric due to cracking or peeling of the print. The exposure rate was determined by printing the sample surface (transfer printing part) with a copying machine and using an image processing device to obtain the ratio of the area of the fabric exposed to the area of the transferred and printed part, and the obtained value was taken as the exposure rate. In Comparative Examples 1, 4, and 5, since the transfer of all inks could not be performed, the washing fastness of the dyed goods could not be evaluated. ◎: The exposure rate of the fabric is 0.1% or less 〇: The exposure rate of the fabric exceeds 0.1% and is 2.0% or less △: The exposure rate of the fabric exceeds 2.0% and is 4.0% or less ×: The exposure rate of the fabric exceeds 4.0%

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

[0228]

Table 2

[0229]

Table 3

[0230]

Table 4

[0231] In Examples 1 to 22 where the glass transition temperature and weight average molecular weight of the resin contained in the adhesive ink were adjusted within a predetermined range, the transferability during transfer printing onto the fabric was excellent, and the wet rubbing fastness and texture of the obtained dyed goods were excellent.

Explanation of symbols

[0232] 100 Transfer medium 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 fabrics, The adhesive ink comprises a resin, a water-soluble organic solvent, and water. The resin is an adhesive ink having a glass transition temperature of 30°C or less and a weight-average molecular weight of 10,000 to 700,000.

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

4. The adhesive ink according to claim 1, wherein the fabric is formed from cotton, polyester fibers, polypropylene fibers, nylon fibers, or a mixture thereof.

5. The adhesive ink according to claim 1, An ink set including colored ink containing pigments and resins.

6. The resin contained in the adhesive ink includes at least one selected from the group consisting of acrylic resins and polyester resins. The ink set according to claim 5, wherein the resin contained in the colored ink includes at least one selected from the group consisting of acrylic resins and polyester resins.

7. A transfer medium on which the adhesive ink described in claim 1 is printed, with or without a colored ink layer formed from a colored ink containing a pigment and a resin, on a transfer substrate.

8. The transfer medium according to claim 7, wherein the transfer substrate is a plastic film or paper.

9. The transfer medium according to claim 7, wherein the transfer medium further has an ink receiving layer on the surface of the transfer substrate on which the adhesive ink is printed.

10. A printed material transferred using the adhesive ink described in claim 1.

11. Step 3 involves printing adhesive ink onto a transfer substrate or onto a colored ink layer laminated on a transfer substrate using an inkjet printer; and, The step 4 includes drying the adhesive ink; The adhesive ink used in step 3 comprises a resin, a water-soluble organic solvent, and water, wherein 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 fabrics.

12. Step 3 is a step of printing adhesive ink onto a colored ink layer laminated on a transfer substrate using an inkjet printer, The manufacturing method according to claim 11, wherein the colored ink layer is formed by step 1 of printing colored ink onto a transfer substrate using an inkjet printer, and step 2 of drying the colored ink.

13. The manufacturing method according to claim 12, wherein step 2 is a step of evaporating 20 to 80% by mass of the 100% by mass of the components of the colored ink excluding the solid components.

14. The manufacturing method according to claim 11, wherein the thickness of the adhesive ink after the drying step 4 is 0.5 to 200 μm.

15. A method for producing a printed fabric, comprising the step of transferring a transfer medium obtained by the manufacturing method described in claim 11 onto a piece of cloth.

16. The transfer printing process includes an adhesion step of bringing the side of the transfer medium on which adhesive ink is printed into close contact with the fabric, and a step of peeling the transfer substrate from the fabric. The manufacturing method according to claim 15, wherein the adhesion time in the adhesion step is 30 seconds or less.

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