Transfer printing ink, ink set for transfer printing, and transfer printing method

Abstract

Provided is a transfer printing ink and an application thereof, the transfer printing ink comprising water, a pigment, a polymer having a crosslinked structure, and resin particles. The content of the resin particles is 5 mass% or more in relation to the total amount of the transfer printing ink.

Description

Transfer printing ink, transfer printing ink set, and transfer printing method

[0001] The present disclosure relates to a transfer printing ink, a transfer printing ink set, and a transfer printing method.

[0002] In recent years, various methods for printing on fabrics have been investigated. For example, Japanese Patent Application Laid-Open No. 2023-87372 describes a printing method for drawing an image on a transfer medium by transferring the image printed on the transfer medium to the transfer medium, the method comprising: a printing step in which an image is printed on the transfer medium using a printing device that performs printing using an inkjet method; a hot-melt resin deposition step in which a hot-melt resin powder, which is a powder containing a resin that softens when heated, is deposited on the transfer medium on which the image has been printed; and a transfer step in which the transfer medium to which the hot-melt resin powder has been deposited is heated and a hot-melt resin portion, which is a resin portion formed by the hot-melt resin powder being softened by heating, is deposited on the transfer medium, thereby transferring the image from the transfer medium to the transfer medium. The printing device includes a colored ink head that is an inkjet head that ejects colored ink, which is an ink containing a colorant that exhibits a colored color, and a clear ink head that is an inkjet head that ejects clear ink, which is a colorless, light-transmitting ink. The printing method further includes ejecting clear ink from the clear ink head onto at least a portion of the area on the transfer medium onto which the colored ink is ejected from the colored ink head during the printing step.

[0003] In transfer printing, there are cases where it is required to improve the ink ejection properties, to provide printed items with excellent washing fastness in warm water, and to prevent the image from peeling off due to washing and drying.

[0004] The present disclosure has been made in view of the above circumstances, and an object of the present invention is to provide a transfer printing ink, a transfer printing ink set, and a transfer printing method that are capable of producing a printed item that has excellent discharge properties, excellent fastness to washing in warm water, and suppresses image peeling due to washing and drying.

[0005] The present disclosure includes the following aspects. <1> A transfer printing ink comprising water, a pigment, a polymer having a crosslinked structure, and resin particles, wherein the content of the resin particles is 5% by mass or more relative to the total amount of the transfer printing ink. <2> The transfer printing ink according to <1>, further comprising an organic solvent having an SP value of 26 or less, wherein the content of the organic solvent having an SP value of 26 or less is 3% by mass or more relative to the total amount of the transfer printing ink. <3> The transfer printing ink according to <1> or <2>, wherein the organic solvent having an SP value of 26 or less is an alkylene glycol alkyl ether. <4> The transfer printing ink according to any one of <1> to <3>, wherein the polymer having a crosslinked structure is crosslinked with an epoxy compound. <5> The transfer printing ink according to any one of <1> to <3>, wherein the glass transition temperature T Ｄ <6> The transfer printing ink according to any one of <1> to <4>, wherein the glass transition temperature T Ｌ <7> The transfer printing ink according to any one of <1> to <5>, wherein the glass transition temperature T Ｄ and the glass transition temperature T Ｌ The transfer printing ink according to any one of <1> to <6> satisfies the following formula (1): Ｄ -T Ｌ≦160°C ... (1) <8> The transfer printing ink according to any one of <1> to <7>, wherein the polymer having a crosslinked structure is a crosslinked product of a polymer in which the content of structural units derived from a polymerizable monomer having at least one hydrophobic group selected from the group consisting of an alkyl group having 10 or more carbon atoms and an aromatic hydrocarbon group is 50% by mass or more. <9> A transfer printing ink set comprising: a transfer printing ink containing water, a pigment, a polymer having a crosslinked structure, and resin particles, wherein the content of the resin particles is 5% by mass or more with respect to the total amount of the transfer printing ink; and an overcoat liquid containing the resin particles. <10> The transfer printing ink set according to <9>, wherein the content of the resin particles in the overcoat liquid is 7% by mass or more with respect to the total amount of the overcoat liquid. <11> The transfer printing ink set according to <9> or <10>, wherein the overcoat liquid contains a softener. <12> A transfer printing ink set comprising the transfer printing ink according to any one of <1> to <8>, and a pretreatment liquid containing a flocculant. <13> A transfer printing ink set comprising the transfer printing ink according to any one of <1> to <8>, an overcoat liquid for transfer printing containing resin particles, and a pretreatment liquid containing a flocculant. <14> A transfer printing method comprising the steps of applying the transfer printing ink according to any one of <1> to <8> onto a non-permeable substrate to record an image, and transferring the image recorded on the non-permeable substrate to a fabric.

[0006] The present disclosure can provide a transfer printing ink, a transfer printing ink set, and a transfer printing method that can produce a printed item that has excellent discharge properties, excellent fastness to washing in warm water, and suppresses image peeling due to washing and drying.

[0007] FIG. 1 is a conceptual diagram of an image recording apparatus used in the examples.

[0008] The transfer printing ink, transfer printing ink set, and transfer printing method of the present disclosure will be described in detail below.

[0009] In this specification, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

[0010] As used herein, the amount of each component in a composition refers to the total amount of the components in the composition unless otherwise specified, when the composition contains multiple substances corresponding to each component. In this specification, a combination of two or more preferred aspects is a more preferred aspect. As used herein, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0011] [Transfer Printing Ink] The transfer printing ink (hereinafter simply referred to as "ink") of the present disclosure contains water, a pigment, a polymer having a crosslinked structure, and resin particles, and the content of the resin particles is 5 mass% or more relative to the total amount of the transfer printing ink. The ink of the present disclosure is an ink used for transfer printing. Specifically, it is an ink used to record an image on a release substrate and transfer the recorded image to a fabric.

[0012] When an image is recorded using the ink of the present disclosure and the recorded image is transferred to a fabric, a printed textile can be obtained that has excellent fastness to washing in warm water and that is inhibited from peeling off when washed and dried. In addition, the ink of the present disclosure has excellent ejection properties.

[0013] The reason for this is not clear, but is speculated as follows.

[0014] The ink of the present disclosure contains a polymer with a crosslinked structure, and the polymer with a crosslinked structure functions as a dispersant for dispersing the pigment. The polymer with a crosslinked structure has excellent adsorption properties for the pigment, and therefore the ink of the present disclosure has excellent ejection properties. Furthermore, the ink of the present disclosure contains a polymer with a crosslinked structure and a resin particle content of 5% by mass or more, which improves the adhesion of the image to the fabric, suppresses image peeling due to washing and drying, and provides excellent fastness to washing in hot water. In particular, it has been found that the inclusion of a polymer with a crosslinked structure improves the breaking strength of the ink film. The high breaking strength of the ink film suppresses image cracking against deformation of the fabric due to external forces applied during hot water washing and drying. It is believed that this results in suppressed image peeling.

[0015] In contrast, Japanese Patent Application Laid-Open No. 2023-87372 does not describe any specific composition of a polymer having a crosslinked structure, resin particles, or their content ratios.

[0016] Each component contained in the ink of the present disclosure will be described below.

[0017] <Water> The ink contains water. The water content is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more, relative to the total amount of the ink. The upper limit of the water content relative to the total amount of the ink is determined appropriately depending on the contents of other components, but is, for example, 99% by mass, preferably 95% by mass, and more preferably 90% by mass.

[0018] Pigment The ink of the present disclosure contains a pigment.

[0019] The pigment may be either an organic pigment or an inorganic pigment that is normally commercially available. Examples of the pigment include those described in "Pigment Dictionary" edited by Seijiro Ito (published in 2000), "Industrial Organic Pigments" by W. Herbst and K. Hunger, and JP-A Nos. 2002-12607, 2002-188025, 2003-26978, and 2003-342503.

[0020] The pigment may be a water-insoluble pigment that can be dispersed in water with the aid of a dispersant, or may be a self-dispersing pigment. A self-dispersing pigment is a pigment that can be dispersed in water without the use of a dispersant. A self-dispersing pigment is a compound in which at least one hydrophilic group selected from the group consisting of a carbonyl group, a hydroxyl group, a carboxyl group, a sulfo group, a phosphate group, and salts thereof is chemically bonded to the surface of the pigment directly or via another group.

[0021] The pigment may be a chromatic color material (for example, cyan, magenta, yellow, etc.) or an achromatic color material (for example, white and black).

[0022] From the viewpoints of image density and ejection performance, the content of the pigment is preferably 2% by mass to 25% by mass, more preferably 3% by mass to 20% by mass, and even more preferably 4% by mass to 15% by mass, relative to the total amount of the ink.

[0023] <Polymer Having a Crosslinked Structure> The ink of the present disclosure contains a polymer having a crosslinked structure. The polymer having a crosslinked structure is not particularly limited as long as it is a polymer having at least one crosslinked structure in the molecule. The polymer having a crosslinked structure preferably functions as a dispersant that disperses the pigment contained in the ink of the present disclosure.

[0024] Whether or not the polymer contained in the ink has a crosslinked structure can be determined, for example, by the following method. First, the ink is subjected to a separation method such as solvent extraction to separate the polymer. The separated polymer is analyzed using various analytical methods such as nuclear magnetic resonance (NMR), infrared spectroscopy (IR), and thermal analysis, allowing a comprehensive determination of whether or not the polymer has a crosslinked structure.

[0025] A polymer having a crosslinked structure (hereinafter referred to as a "crosslinked polymer") is, for example, a crosslinked body formed by crosslinking an uncrosslinked polymer with a crosslinking agent. The uncrosslinked polymer is preferably a water-soluble polymer.

[0026] In the present disclosure, the term "water-soluble" in "water-soluble polymer" means that the amount of the polymer that dissolves in 100 g of distilled water at 25° C. is 2 g or more. The amount of the water-soluble polymer that dissolves in 100 g of distilled water at 25° C. is preferably 5 g or more, and more preferably 10 g or more.

[0027] The uncrosslinked polymer is preferably a polymer having a functional group that can be crosslinked by a crosslinking agent. Examples of the crosslinkable functional group include a carboxy group or a salt thereof, an isocyanate group, and an epoxy group. Among these, from the viewpoint of improving the dispersibility of the pigment, the crosslinkable functional group is preferably a carboxy group or a salt thereof, and a carboxy group is particularly preferred. That is, the uncrosslinked polymer is preferably a polymer containing a carboxy group.

[0028] The uncrosslinked polymer is preferably a copolymer containing a structural unit derived from a polymerizable monomer containing a carboxy group (hereinafter referred to as a "carboxy group-containing monomer"). The structural unit derived from the carboxy group-containing monomer contained in the copolymer may be of only one type, or may be of two or more types. The copolymer may be a random copolymer or a block copolymer, but is preferably a random copolymer.

[0029] Examples of carboxy group-containing monomers include (meth)acrylic acid, β-carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid, and crotonic acid.

[0030] From the viewpoint of crosslinkability and dispersibility, the carboxy group-containing monomer is preferably (meth)acrylic acid or β-carboxyethyl acrylate, and more preferably (meth)acrylic acid.

[0031] The uncrosslinked polymer preferably contains a structural unit derived from a polymerizable monomer having a hydrophobic group (hereinafter also referred to as a "hydrophobic monomer") in addition to the structural unit derived from the carboxyl group-containing monomer. The structural unit derived from the hydrophobic monomer contained in the copolymer may be of only one type or of two or more types.

[0032] From the viewpoint of adsorption to the pigment, the hydrophobic monomer is preferably a polymerizable monomer having at least one hydrophobic group selected from the group consisting of an alkyl group having 10 or more carbon atoms and an aromatic hydrocarbon group.

[0033] The polymerizable group contained in the hydrophobic monomer is preferably an ethylenically unsaturated group, more preferably a vinyl group, an allyl group, or a (meth)acryloyl group, and even more preferably a (meth)acryloyl group.

[0034] From the viewpoint of pigment adsorption, the uncrosslinked polymer preferably has a content of structural units derived from hydrophobic monomers of 50% by mass or more. The content of structural units derived from hydrophobic monomers in the uncrosslinked polymer is more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the content of structural units derived from hydrophobic monomers is, for example, 90% by mass.

[0035] The number of carbon atoms in the monomer having an alkyl group having 10 or more carbon atoms is preferably 10 to 22, and more preferably 10 to 18.

[0036] The alkyl group in the monomer having an alkyl group having 10 or more carbon atoms may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. From the viewpoint of adsorption to the pigment, the alkyl group is preferably a linear alkyl group.

[0037] Examples of monomers having an alkyl group having 10 or more carbon atoms include dodecyl (meth)acrylate (also known as lauryl (meth)acrylate), tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), hexadecyl (meth)acrylate, octadecyl (meth)acrylate (also known as stearyl (meth)acrylate), eicosyl (meth)acrylate, and docosyl (meth)acrylate (also known as behenyl (meth)acrylate).

[0038] Examples of the aromatic hydrocarbon group in the aromatic hydrocarbon group-containing monomer include a phenyl group and a naphthyl group, and examples of the aromatic hydrocarbon group-containing monomer include styrene, α-methylstyrene, 2-naphthyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate.

[0039] The uncrosslinked polymer is preferably a random copolymer containing a structural unit derived from a carboxy group-containing monomer and a structural unit derived from a hydrophobic monomer, more preferably a random copolymer containing a structural unit derived from (meth)acrylic acid and a structural unit derived from a hydrophobic monomer, and particularly preferably a random copolymer containing a structural unit derived from (meth)acrylic acid and a structural unit derived from benzyl (meth)acrylate.

[0040] The acid value of the uncrosslinked polymer is preferably from 65 mgKOH / g to 220 mgKOH / g, more preferably from 65 mgKOH / g to 170 mgKOH / g, from the viewpoint of pigment dispersibility.

[0041] Furthermore, from the viewpoint of improving the quality of the recorded image, the acid value of the crosslinked polymer is preferably 20 mgKOH / g to 205 mgKOH / g, more preferably 30 mgKOH / g to 180 mgKOH / g, and even more preferably 65 mgKOH / g to 140 mgKOH / g.

[0042] The weight average molecular weight (Mw) of the uncrosslinked polymer is not particularly limited, but from the viewpoint of pigment dispersibility, it is preferably 3,000 to 300,000, more preferably 5,000 to 200,000, and even more preferably 7,000 to 100,000.

[0043] The preferred range of the weight average molecular weight of the crosslinked polymer is the same as the preferred range of the weight average molecular weight of the uncrosslinked polymer.

[0044] In the present disclosure, the weight-average molecular weight is measured using gel permeation chromatography (GPC). For example, an HLC-8220GPC (manufactured by Tosoh Corporation) is used as the GPC, three TSKgel Super Multipore HZ-H columns (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) are used as the columns, and THF (tetrahydrofuran) is used as the eluent. The conditions are a sample concentration of 0.45 mass%, a flow rate of 0.35 ml / min, a sample injection volume of 10 μL, a measurement temperature of 40°C, and detection using a differential refractive index (RI) detector. A calibration curve is prepared using eight samples of "TSK Standard Polystyrene" manufactured by Tosoh Corporation under the product names: "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", "A-1000", and "n-propylbenzene" as standard samples.

[0045] The crosslinking agent used to crosslink the uncrosslinked polymer is preferably a compound having two or more reactive sites with the uncrosslinked polymer (e.g., a polymer having a carboxy group). Only one type of crosslinking agent may be used, or two or more types may be used.

[0046] From the viewpoint of reactivity, the crosslinking agent is preferably an epoxy compound, i.e., the crosslinked polymer is preferably crosslinked with an epoxy compound.

[0047] Whether the crosslinked polymer is crosslinked with an epoxy compound can be confirmed by measuring the acid value and by GC / MS analysis.

[0048] A preferred combination of a crosslinking agent and an uncrosslinked polymer is a combination of a compound having two or more epoxy groups (i.e., a bifunctional or higher epoxy compound) and a polymer having a carboxy group. In this combination, a crosslinked structure is formed by reaction between the epoxy group and the carboxy group. The formation of the crosslinked structure by the crosslinking agent is preferably carried out after the pigment has been dispersed by the uncrosslinked polymer.

[0049] Examples of difunctional or higher functional epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether.

[0050] Among these, the difunctional or higher epoxy compound is preferably polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, or trimethylolpropane triglycidyl ether.

[0051] The crosslinking agent may be a commercially available product, such as Denacol EX-321, EX-521, EX-821, EX-830, EX-850, EX-851, and EX-861 (manufactured by Nagase ChemteX Corporation).

[0052] The molar ratio of the reactive site (e.g., epoxy group) in the crosslinking agent to the reactive site (e.g., carboxy group) in the uncrosslinked polymer is preferably 1:1.1 to 1:10, more preferably 1:1.1 to 1:5, and even more preferably 1:1.1 to 1:3, from the viewpoints of the crosslinking reaction rate and the dispersion stability after crosslinking.

[0053] Glass transition temperature T of crosslinked polymer ＤThe glass transition temperature T is preferably 50° C. or higher, and more preferably 70° C. or higher, from the viewpoints of improving the fastness to washing in hot water and further suppressing peeling of the image due to washing and drying. Ｄ The upper limit is, for example, 140°C.

[0054] In the present disclosure, the glass transition temperature is measured using a differential scanning calorimeter, for example, a product named "DSC-60" manufactured by Shimadzu Corporation.

[0055] Resin Particles The ink of the present disclosure contains resin particles. Here, the resin particles are distinguished from the polymer having a crosslinked structure in that they are particles made of resin.

[0056] The resin constituting the resin particles is preferably a water-insoluble polymer. The term "water-insoluble" in the context of a water-insoluble polymer means that the amount of the polymer that dissolves in 100 g of distilled water at 25° C. is less than 2 g.

[0057] Glass transition temperature T of resin particles Ｌ From the viewpoint of film-forming properties, the glass transition temperature T is preferably 30° C. or less, more preferably 10° C. or less, and even more preferably 0° C. or less. Ｌ The lower limit is, for example, −60° C.

[0058] The resin particles are preferably particles made of acrylic resin, particles made of styrene-acrylic resin, particles made of polyester, particles made of urethane resin, particles made of styrene-butadiene copolymer, or particles made of polyolefin resin.

[0059] The resin particles are preferably self-dispersing resin particles. Examples of the self-dispersing resin particles include the self-dispersing polymer particles described in paragraphs 0062 to 0076 of JP 2016-188345 A and paragraphs 0109 to 0140 of WO 2013 / 180074 A.

[0060] The molecular weight of the resin in the resin particles is preferably 1,000 to 300,000, more preferably 2,000 to 200,000, and even more preferably 5,000 to 100,000, in terms of weight average molecular weight.

[0061] The volume average particle size of the resin particles is preferably 1 nm to 200 nm, more preferably 3 nm to 200 nm, and even more preferably 5 nm to 50 nm.

[0062] In the present disclosure, the volume average particle size refers to a value measured using a laser diffraction / scattering particle size distribution analyzer. Examples of the measuring device include a particle size distribution analyzer "Microtrac MT-3300II" (manufactured by Nikkiso Co., Ltd.).

[0063] The content of the resin particles is 5% by mass or more, and preferably 7% by mass or more, based on the total amount of the ink. When the content of the resin particles is 5% by mass or more, excellent abrasion resistance is achieved. From the viewpoint of ejection stability, the content of the resin particles is preferably 13% by mass or less, and more preferably 10% by mass or less.

[0064] Glass transition temperature T of cross-linked polymer Ｄ and the glass transition temperature T Ｌ It is preferable that the following formula (1) is satisfied: 50°C≦T Ｄ -T Ｌ ≦160° C. ... (1)

[0065] "T Ｄ -T Ｌ When "T" is 50°C or higher, the crosslinked polymer has a relatively high glass transition temperature, which improves the breaking strength, and the resin particles have a relatively low glass transition temperature, which provides excellent film-forming properties, and the synergistic effect of both makes it possible to achieve good washing fastness. Ｄ -T Ｌ When the temperature is 160° C. or less, peeling of the image due to washing and drying is further suppressed.

[0066] "T Ｄ -T Ｌ " is more preferably 70°C to 110°C.

[0067] <Organic Solvent Having an SP Value of 26 or Less> The ink of the present disclosure preferably contains an organic solvent having an SP value of 26 or less (hereinafter also referred to as "organic solvent A").

[0068] In the present disclosure, the SP value refers to a value expressed as the square root of the molecular cohesive energy (solubility parameter), and is a value calculated by the method described in R. F. Fedors, Polymer Engineering Science, 14, pp. 147-154 (1974). In the present disclosure, the unit of the SP value is MPa. １／２ was used.

[0069] Examples of organic solvents and their SP values ​​are given below. The values ​​in parentheses indicate the SP value. Propylene glycol (27.6 MPa １／２ ) Ethylene glycol (30.3 MPa １／２ ) Diethylene glycol (30.6 MPa １／２ , triethylene glycol (27.8 MPa １／２ ) Tripropylene glycol (24.7 MPa １／２ ) 2-methyl-1,3-butanediol (28.4) 1,2-pentanediol (25.0 MPa １／２ ) 1,5-pentanediol (29.0 MPa １／２ ) 1,2-hexanediol (24.1 MPa １／２ ) 1,6-hexanediol (27.7 MPa １／２ ) Glycerin (33.5 MPa １／２ ) Methanol (28.2 MPa １／２ ) Isopropyl alcohol (23.7 MPa １／２ ) Triethanolamine (32.4 MPa １／２ ) Dipropylene glycol (27.1 MPa １／２ ) Ethylene glycol monoethyl ether (23.5 MPa １／２ ) Ethylene glycol monopropyl ether (22.7 MPa １／２ ) Ethylene glycol monobutyl ether (22.1 MPa １／２ ) Diethylene glycol monomethyl ether (23.0 MPa １／２ ) Diethylene glycol monoethyl ether (22.4 MPa １／２ ) Diethylene glycol monopropyl ether (21.9 MPa １／２ ) Diethylene glycol monobutyl ether (21.5 MPa １／２) Triethylene glycol monomethyl ether (22.1 MPa １／２ ) Triethylene glycol monoethyl ether (21.7 MPa １／２ ) Triethylene glycol monobutyl ether (21.1 MPa １／２ ) Propylene glycol monomethyl ether (23.1 MPa １／２ ) Propylene glycol monoethyl ether (22.3 MPa １／２ ) Propylene glycol monopropyl ether (21.8 MPa １／２ ) Propylene glycol monobutyl ether (21.4 MPa １／２ ) Dipropylene glycol monomethyl ether (21.3 MPa １／２ ) Dipropylene glycol monopropyl ether (20.7 MPa １／２ ) Dipropylene glycol monobutyl ether (20.5 MPa １／２ ) Dipropylene glycol t-butyl ether (20.0 MPa １／２ ) Tripropylene glycol monomethyl ether (20.4 MPa １／２ ) Diethylene glycol monohexyl ether (20.9 MPa １／２ ) Ethylene glycol mono-2-ethylhexyl ether (20.5 MPa １／２ ) Diethylene glycol mono-2-ethylhexyl ether (20.3 MPa １／２ )

[0070] From the viewpoint of the film-forming properties of the ink film to be formed, organic solvent A is preferably an alkylene glycol alkyl ether, and more preferably a diethylene glycol monoalkyl ether, a propylene glycol monoalkyl ether, a dipropylene glycol monoalkyl ether, or a tripropylene glycol monoalkyl ether.

[0071] The content of organic solvent A is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total amount of the ink. The upper limit of the content of organic solvent A is, for example, 40% by mass.

[0072] The ink of the present disclosure may contain an organic solvent having an SP value of greater than 26, i.e., an organic solvent other than organic solvent A. The content of the other organic solvent is preferably 2% by mass to 30% by mass, more preferably 3% by mass to 20% by mass, and even more preferably 5% by mass to 15% by mass, relative to the total amount of the ink.

[0073] The ink of the present disclosure may contain additives such as surfactants, co-sensitizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, and basic compounds, as needed.

[0074] [Transfer Printing Ink Set] A first embodiment of the transfer printing ink set (hereinafter also referred to as "ink set") of the present disclosure comprises the ink of the present disclosure and an overcoat liquid containing resin particles.

[0075] A second aspect of the ink set of the present disclosure comprises the ink of the present disclosure and a pretreatment liquid containing an aggregating agent.

[0076] A third aspect of the ink set of the present disclosure includes the ink of the present disclosure, an overcoat liquid for transfer printing containing resin particles, and a pretreatment liquid containing a flocculant.

[0077] Details of the inks in the first, second, and third aspects of the ink set of the present disclosure are as described above.

[0078] <First Aspect> The pretreatment liquid contains at least one flocculant.

[0079] (Flocculant) The flocculant is preferably at least one selected from the group consisting of polyvalent metal compounds, organic acids, metal complexes, and cationic polymers, and more preferably contains an organic acid.

[0080] -Polyvalent Metal Compound- Examples of polyvalent metal compounds include salts of alkaline earth metals of Group 2 of the periodic table (e.g., magnesium, calcium), transition metals of Group 3 of the periodic table (e.g., lanthanum), metals of Group 13 of the periodic table (e.g., aluminum), and lanthanides (e.g., neodymium).

[0081] The salts of these metals are preferably salts of organic acids, nitrates, chlorides, or thiocyanates, as described below.

[0082] Among these, the polyvalent metal compound is preferably a calcium salt or magnesium salt of an organic acid (e.g., formic acid, acetic acid, benzoic acid, etc.); a calcium salt or magnesium salt of nitric acid; calcium chloride, magnesium chloride, or a calcium salt or magnesium salt of thiocyanic acid.

[0083] It is preferable that the polyvalent metal compound is at least partially dissociated into polyvalent metal ions and counter ions in the pretreatment liquid.

[0084] Organic Acids Examples of organic acids include organic compounds having an acidic group.

[0085] Acidic groups include phosphate groups, phosphonate groups, phosphinate groups, sulfate groups, sulfonate groups, sulfinate groups, and carboxy groups.

[0086] Among these, from the viewpoint of the aggregation speed of the ink, the acidic group is preferably a phosphate group or a carboxy group, and more preferably a carboxy group.

[0087] It is preferable that at least a portion of the acidic groups is dissociated in the pretreatment liquid.

[0088] Examples of organic compounds having a carboxy group include (meth)acrylic acid, poly(meth)acrylic acid, acetic acid, formic acid, benzoic acid, glycolic acid, malonic acid, malic acid (preferably DL-malic acid), maleic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, fumaric acid, citric acid, tartaric acid, phthalic acid, 4-methylphthalic acid, lactic acid, pyrrolidonecarboxylic acid, pyronecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, pyridinecarboxylic acid, coumaric acid, thiophenecarboxylic acid, and nicotinic acid.

[0089] Among these, from the viewpoint of the aggregation speed of the ink, the organic compound having a carboxy group is preferably a divalent or higher carboxylic acid (hereinafter also referred to as a polycarboxylic acid), and more preferably a dicarboxylic acid.

[0090] Specifically, the polycarboxylic acid is preferably malonic acid, malic acid, maleic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, fumaric acid, tartaric acid, 4-methylphthalic acid, or citric acid, and more preferably malonic acid, malic acid, tartaric acid, succinic acid, glutaric acid, pimelic acid, adipic acid, or citric acid.

[0091] The organic acid preferably has a low pKa (for example, 1.0 to 5.0), which reduces the surface charge of particles such as pigments and resin particles in the ink, which are stabilized by weakly acidic functional groups such as carboxyl groups, by contacting them with an organic acid having an even lower pKa, thereby lowering dispersion stability.

[0092] The organic acid preferably has a low pKa, high solubility in water, and a valence of at least 2. Furthermore, the organic acid more preferably has a high buffering capacity in a pH range lower than the pKa of the functional group (e.g., carboxy group) that stabilizes the dispersion of the particles in the ink.

[0093] -Metal Complex- The metal complex preferably contains, as a metal element, at least one selected from the group consisting of zirconium, aluminum, and titanium.

[0094] The metal complex is preferably a metal complex containing, as a ligand, at least one selected from the group consisting of acetate, acetylacetonate, methylacetoacetate, ethylacetoacetate, octylene glycolate, butoxyacetylacetonate, lactate, lactate ammonium salt, and triethanolamine.

[0095] The metal complex may be a commercially available product. Various organic ligands, particularly various polydentate ligands capable of forming metal chelate catalysts, are commercially available. Therefore, the metal complex may be a metal complex prepared by combining a commercially available organic ligand with a metal.

[0096] Examples of the metal complex include zirconium tetraacetylacetonate (e.g., "Orgatix ZC-150" manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium monoacetylacetonate (e.g., "Orgatix ZC-540" manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium bisacetylacetonate (e.g., "Orgatix ZC-550" manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium monoethylacetoacetate (e.g., "Orgatix ZC-560" manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium acetate (e.g., "Orgatix ZC-115" manufactured by Matsumoto Fine Chemical Co., Ltd.), titanium diisopropoxybis(acetylacetonate) (e.g., "Orgatix TC-100" manufactured by Matsumoto Fine Chemical Co., Ltd.), and titanium tetraacetylacetonate (e.g., "Orgatix" manufactured by Matsumoto Fine Chemical Co., Ltd.). TC-401"), titanium dioctyloxybis(octylene glycolate) (e.g., Matsumoto Fine Chemical Co., Ltd.'s "Orgatix TC-200"), titanium diisopropoxybis(ethyl acetoacetate) (e.g., Matsumoto Fine Chemical Co., Ltd.'s "Orgatix TC-750"), zirconium tetraacetylacetonate (e.g., Matsumoto Fine Chemical Co., Ltd.'s "Orgatix ZC-700"), zirconium tributoxymonoacetylacetonate (e.g., Matsumoto Fine Chemical Co., Ltd.'s "Orgatix ZC-540"), zirconium monobutoxyacetylacetonate bis(ethyl acetoacetate) (e.g., Matsumoto Fine Chemical Co., Ltd.'s "Orgatix ZC-570")), zirconium dibutoxy Bis(ethylacetoacetate) (e.g., "Orgatix ZC-580" manufactured by Matsumoto Fine Chemical Co., Ltd.), aluminum trisacetylacetonate (e.g., "Orgatix AL-80" manufactured by Matsumoto Fine Chemical Co., Ltd.), titanium lactate ammonium salt (e.g., "Orgatix TC-300" manufactured by Matsumoto Fine Chemical Co., Ltd.), titanium lactate (e.g., "Orgatix TC-310, 315" manufactured by Matsumoto Fine Chemical Co., Ltd.), titanium triethanolamine (e.g., "Orgatix TC-400" manufactured by Matsumoto Fine Chemical Co., Ltd.), and zirconyl chloride compounds (e.g.,Matsumoto Fine Chemical Co., Ltd.'s "Orgatics ZC-126").

[0097] Among these, the metal complex is preferably a titanium lactate ammonium salt (e.g., "Orgatix TC-300" manufactured by Matsumoto Fine Chemical Co., Ltd.), titanium lactate (e.g., "Orgatix TC-310, 315" manufactured by Matsumoto Fine Chemical Co., Ltd.), titanium triethanolamine (e.g., "Orgatix TC-400" manufactured by Matsumoto Fine Chemical Co., Ltd.), or a zirconyl chloride compound (e.g., "Orgatix ZC-126" manufactured by Matsumoto Fine Chemical Co., Ltd.).

[0098] -Cationic Polymer- The pretreatment liquid may also contain one or more cationic polymers as a flocculating component. The cationic polymer is preferably a homopolymer of a cationic monomer having a primary to tertiary amino group or a quaternary ammonium salt group, or a copolymer or condensation polymer of a cationic monomer and a non-cationic monomer. The cationic polymer may be used in the form of either a water-soluble polymer or water-dispersible latex particles. Examples of cationic polymers include polyvinylpyridine salts, polyalkylaminoethyl acrylates, polyalkylaminoethyl methacrylates, polyvinylimidazole, polyethyleneimines, polybiguanides, polyguanides, polyallylamine, and derivatives thereof.

[0099] The weight-average molecular weight of the cationic polymer is preferably small from the viewpoint of the viscosity of the pretreatment liquid. When the pretreatment liquid is applied to a recording medium by an inkjet recording method, the weight-average molecular weight is preferably 1,000 to 500,000, more preferably 1,500 to 200,000, and even more preferably 2,000 to 100,000. A weight-average molecular weight of 1,000 or more is advantageous from the viewpoint of aggregation speed. A weight-average molecular weight of 500,000 or less is advantageous from the viewpoint of ejection reliability. However, this does not apply when the pretreatment liquid is applied to a recording medium by a method other than inkjet recording.

[0100] The content of the flocculant is preferably 0.1% by mass to 40% by mass, more preferably 0.1% by mass to 30% by mass, even more preferably 1% by mass to 20% by mass, and particularly preferably 1% by mass to 10% by mass, relative to the total amount of the pretreatment liquid.

[0101] The pretreatment liquid may contain other components in addition to the flocculant, as necessary. Examples of other components that can be contained in the pretreatment liquid include known additives such as organic solvents, resin particles, surfactants, solid wetting agents, colloidal silica, inorganic salts, anti-fading agents, emulsion stabilizers, penetration enhancers, UV absorbers, preservatives, antifungal agents, pH adjusters, viscosity adjusters, rust inhibitors, chelating agents, and water-soluble polymer compounds (for example, the water-soluble polymer compounds described in paragraphs 0026 to 0080 of JP 2013-001854 A).

[0102] <Second Aspect> The overcoat liquid contains at least one type of resin particles.

[0103] Examples of resin particles contained in the overcoat liquid include the same resin particles contained in the ink. Among them, from the viewpoints of image transferability and adhesion to the substrate, the resin particles contained in the overcoat liquid are preferably particles made of a urethane resin or particles made of a styrene-acrylic resin.

[0104] The content of the resin particles is preferably 7% by mass or more, more preferably 10% by mass or more, based on the total amount of the overcoat liquid from the viewpoints of image transferability and adhesion to the substrate, and the upper limit of the content of the resin particles is, for example, 20% by mass from the viewpoint of ejection properties.

[0105] The overcoat liquid preferably contains a cationic surfactant. Many commercially available fabric softeners (specifically, fabric softeners for clothing) contain a cationic surfactant. Therefore, it is preferable to add a fabric softener to the overcoat liquid to allow the overcoat liquid to contain the cationic surfactant.

[0106] When the overcoat liquid contains a cationic surfactant, the cationic surfactant contained in the fabric softener softens the texture of the fabric. The cationic surfactant is not particularly limited, and conventionally known surfactants can be used. Examples of cationic surfactants include alkylamine salts, quaternary ammonium salts, alkylimidazolinium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

[0107] (Other Components) The overcoat liquid may contain other components in addition to the resin particles and softener, as necessary. Examples of other components that can be contained in the overcoat liquid include known additives such as organic solvents, surfactants, solid wetting agents, colloidal silica, inorganic salts, anti-fading agents, emulsion stabilizers, penetration enhancers, UV absorbers, preservatives, antifungal agents, pH adjusters, viscosity adjusters, rust inhibitors, chelating agents, and water-soluble polymer compounds (for example, the water-soluble polymer compounds described in paragraphs 0026 to 0080 of JP 2013-001854 A).

[0108] <Third Aspect> Preferred aspects of the pre-treatment liquid and overcoat liquid in the third aspect are the same as the preferred aspects of the pre-treatment liquid in the first aspect and the preferred aspects of the overcoat liquid in the second aspect.

[0109] [Transfer Printing Method] The transfer printing method of the present disclosure includes a step of applying the ink of the present disclosure onto a non-permeable substrate to record an image (hereinafter also referred to as an "ink application step"), and a step of transferring the image recorded on the non-permeable substrate to a fabric (hereinafter also referred to as a "transfer step").

[0110] <Ink Application Step> The transfer printing method of the present disclosure includes a step of applying the ink of the present disclosure onto an impermeable substrate to record an image.

[0111] In the present disclosure, the term "impermeability" in an impermeable substrate refers to a property in which the water absorption rate over 24 hours measured in accordance with ASTM D570-98 (2018) is 2.5% or less. Here, the unit of water absorption rate, "%", is based on mass. The water absorption rate is preferably 1.0% or less, and more preferably 0.5% or less.

[0112] Examples of materials for the impermeable substrate include glass, metals (e.g., aluminum, zinc, copper, etc.), and resins (e.g., polyvinyl chloride, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, nylon, acrylic resin, etc.).

[0113] The material of the impermeable substrate is preferably a resin, that is, the impermeable substrate is preferably a resin substrate.

[0114] Among these, from the viewpoint of versatility, the material of the impermeable substrate is preferably polypropylene, polyethylene, polyethylene terephthalate, nylon, acrylic resin, or polyvinyl chloride.

[0115] The shape of the impermeable substrate is preferably a sheet (film) or plate, and examples of such a shape of the impermeable substrate include a glass plate, a metal plate, a resin sheet (resin film), a plastic-laminated paper, a metal-laminated or metal-deposited paper, and a metal-laminated or metal-deposited plastic sheet (plastic film).

[0116] Examples of impermeable resin substrates include resin sheets (resin films). In particular, commercially available resin sheets for DTF printing are preferred, and specifically, DTF-H60 (manufactured by Celcam Co., Ltd.) and the like can be used.

[0117] The thickness of the impermeable substrate is preferably 0.1 μm to 1,000 μm, more preferably 0.1 μm to 800 μm, and even more preferably 1 μm to 500 μm.

[0118] The non-permeable substrate may be subjected to a hydrophilization treatment. Examples of hydrophilization treatments include, but are not limited to, corona treatment, plasma treatment, flame treatment, heat treatment, abrasion treatment, light irradiation treatment (e.g., UV treatment), and flame treatment. Corona treatment can be carried out using, for example, a Corona Master (product name "PS-10S", manufactured by Shinko Electric Meter Co., Ltd.). The conditions for the corona treatment may be appropriately selected depending on the type of non-permeable substrate, etc.

[0119] <Application of Ink> The application of ink can be carried out by applying a known application method such as a coating method, an ink jet recording method, or a dipping method.

[0120] Examples of the coating method include known coating methods using a bar coater, extrusion die coater, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, reverse roll coater, and the like.

[0121] There are no particular limitations on the ink ejection method used in inkjet recording, and any of the well-known methods may be used, such as a charge control method that uses electrostatic attraction to eject ink, a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezoelectric element, an acoustic inkjet method that converts an electric signal into an acoustic beam and irradiates the ink with it, thereby ejecting the ink using radiation pressure, and a thermal inkjet (Bubble Jet (registered trademark)) method that heats the ink to form bubbles and uses the resulting pressure.

[0122] As an inkjet recording method, in particular, the method described in JP-A-54-59936 can be effectively used, in which ink subjected to the action of thermal energy undergoes a sudden change in volume, and the ink is ejected from the nozzles by the force caused by this state change. As an inkjet recording method, the method described in paragraphs 0093 to 0105 of JP-A-2003-306623 can also be applied.

[0123] Application of ink to a non-permeable substrate by ink jet recording is carried out by ejecting the ink from the nozzles of an ink jet head.

[0124] Inkjet head methods include the shuttle method, in which a short serial head is scanned across the width of the recording medium to perform recording, and the line method, which uses a line head in which recording elements are arranged to cover the entire area of ​​one side of the recording medium.

[0125] The line method allows for image recording over the entire surface of a recording medium by scanning the recording medium in a direction intersecting the arrangement direction of the recording elements. The line method eliminates the need for a transport system, such as a carriage that scans a short head, as in the shuttle method. Furthermore, compared to the shuttle method, the line method does not require complex scanning control of the carriage movement and the recording medium, and only the recording medium moves. Therefore, the line method achieves faster image recording speeds than the shuttle method.

[0126] The ink is preferably applied using an inkjet head having a resolution of 300 dpi or more (more preferably 600 dpi or more, and even more preferably 800 dpi or more), where dpi stands for dots per inch, and 1 inch is 2.54 cm.

[0127] The amount of ink droplets ejected from the nozzles of the inkjet head is preferably 1 pL (picoliter) to 10 pL, more preferably 1.5 pL to 6 pL, from the viewpoint of obtaining a high-definition image. Furthermore, from the viewpoint of improving image unevenness and continuous gradation, it is also effective to eject droplets of different amounts in combination.

[0128] <Transfer Step> The transfer printing method of the present disclosure includes a step of transferring an image recorded on an impermeable substrate to a fabric.

[0129] Examples of fiber types in the fabric include synthetic fibers such as nylon, polyester, and acrylonitrile; semi-synthetic fibers such as acetate and rayon; natural fibers such as cotton, silk, and wool; and mixed fibers consisting of two or more types selected from the group consisting of synthetic fibers, semi-synthetic fibers, and natural fibers.

[0130] The fiber type in the fabric is preferably cellulose fiber, more preferably cotton. The fabric may be in the form of a woven fabric, a knitted fabric, a nonwoven fabric, etc. The fabric may be a fabric for a fabric product.

[0131] Examples of fabric products include clothing (for example, T-shirts, sweatshirts, jerseys, pants, sweatsuits, dresses, blouses, etc.), bedding, handkerchiefs, etc.

[0132] An example of a method for transferring an image to a fabric is to overlap an impermeable substrate on which an image has been recorded and a fabric in a state where the image and the fabric are in contact with each other, and then heat the overlapped substrate. The heating temperature is, for example, 100° C. to 200° C. The heating time is, for example, 20 seconds to 5 minutes.

[0133] A commercially available heat press can be used for the transfer, such as an automatic tabletop flat press AF-54TEN model (manufactured by Asahi Textile Machinery Co., Ltd.) or Zeus PZ-130110D (manufactured by Europort).

[0134] In the transfer step, it is preferable to apply a hot melt adhesive to the surface of the non-permeable substrate on which the image is recorded before superimposing the non-permeable substrate on the fabric, in order to improve adhesion.

[0135] <Other Steps> The transfer printing method of the present disclosure preferably further includes a step of applying a pretreatment liquid onto the non-permeable substrate (hereinafter also referred to as a "pretreatment liquid applying step"), and preferably applies an ink onto the non-permeable substrate to which the pretreatment liquid has been applied.

[0136] Details of the pretreatment liquid are as described above. The pretreatment liquid can be applied by a known application method such as a coating method, an inkjet recording method, or a dipping method.

[0137] Examples of the coating method include known coating methods using a bar coater, extrusion die coater, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, reverse roll coater, and the like.

[0138] Details of the inkjet recording method are the same as those of the inkjet recording method in the ink application step.

[0139] Before applying the pretreatment liquid, the non-permeable substrate may be heated. The heating temperature may be appropriately set depending on the type of non-permeable substrate and the composition of the pretreatment liquid, but the temperature of the non-permeable substrate is preferably 30°C to 70°C, and more preferably 30°C to 60°C.

[0140] In the pretreatment liquid application step, the pretreatment liquid applied to the non-permeable substrate may be dried by heating. Examples of means for drying the pretreatment liquid by heating include known heating means such as a heater, known air blowing means such as a dryer, and a combination of these.

[0141] Examples of methods for heating and drying the pretreatment liquid include a method of applying heat using a heater or the like from the side opposite to the surface of the non-permeable substrate to which the pretreatment liquid has been applied, a method of applying warm air or hot air to the surface of the non-permeable substrate to which the pretreatment liquid has been applied, a method of applying heat using an infrared heater from the side of the non-permeable substrate to which the pretreatment liquid has been applied or the side opposite to the surface to which the pretreatment liquid has been applied, and a combination of these methods.

[0142] The heating temperature during heating and drying of the pretreatment liquid is preferably 35° C. or higher, and more preferably 40° C. or higher. There is no particular upper limit to the heating temperature, but it is preferably 100° C., more preferably 90° C., and even more preferably 70° C.

[0143] The time for heat drying is not particularly limited, but is preferably 0.5 to 60 seconds, more preferably 0.5 to 20 seconds, and even more preferably 0.5 to 10 seconds.

[0144] The transfer printing method of the present disclosure may include, after the ink application step, a step of applying an overcoat liquid onto the ink-applied surface of the non-permeable substrate (hereinafter also referred to as an "overcoat liquid application step"). The transfer printing method of the present disclosure may also include a pretreatment liquid application step, an ink application step, and an overcoat liquid application step.

[0145] The details of the overcoat liquid are as described above. The overcoat liquid can be applied by applying a known application method such as a coating method, an inkjet recording method, a dipping method, etc. When the transfer printing method of the present disclosure includes the overcoat liquid application step, the above-mentioned step of applying a hot melt adhesive (hereinafter also referred to as the "hot melt adhesive application step") can be omitted.

[0146] Hereinafter, the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited to the following examples as long as it does not depart from the gist of the disclosure.

[0147] <<Example 1>> [Ink Preparation] <Synthesis of Uncrosslinked Polymer d1> A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 153.5 parts by mass of tripropylene glycol monomethyl ether (product name "MFTG", manufactured by Nippon Nyukazai Co., Ltd.) as a reaction solvent, and the atmosphere inside the reaction vessel was then purged with nitrogen gas. Next, the reaction vessel was heated to 85°C, and a mixture of MFTG (76.8 parts by mass) as a reaction solvent, raw material monomers (100 parts by mass in total) of the types and mass ratios shown in Table 1, and V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (3.0 parts by mass) as a polymerization initiator was added dropwise over 3 hours to carry out a polymerization reaction. After completion of the dropwise addition, the reaction was continued for an additional 3 hours at 85°C to complete the polymerization, yielding a solution containing uncrosslinked polymer d1.

[0148] <Preparation of Uncrosslinked Dispersion of Magenta Pigment> A mixture of the following composition was pre-dispersed to a uniform consistency, and then dispersed for 3 hours using a bead mill (Star Mill manufactured by Ashizawa Finetex Co., Ltd., bead diameter: 0.3 mmφ, zirconia beads), to obtain an uncrosslinked dispersion in which the magenta pigment was dispersed by the uncrosslinked polymer.

[0149] Magenta pigment: Pigment Red 122... 120 parts by mass MFTG solution of uncrosslinked polymer d1 (30% by mass solids concentration)... 120.0 parts by mass MFTG... 6.0 parts by mass 1 / mol / L aqueous sodium hydroxide solution... 125.8 parts by mass Water... 230.0 parts by mass

[0150] While stirring a mixture of the following composition with a magnetic stirrer, a mixture of 1 mol / L hydrochloric acid aqueous solution and pure water was added over 5 minutes to change the degree of neutralization from 80% to 60%. After mixing, the mixture was stirred with a magnetic stirrer for 60 minutes.

[0151] Uncrosslinked dispersion diluted with ion-exchanged water to a pigment concentration of 15% by mass: 500.0 parts by mass; 1 mol / L hydrochloric acid aqueous solution: 19.4 parts by mass; Pure water: 225.2 parts by mass

[0152] <Preparation of Crosslinked Dispersion of Magenta Pigment> A mixture having the following composition was reacted at 70°C for 6 hours and then cooled to 25°C, thereby crosslinking the uncrosslinked polymer d1 in the uncrosslinked dispersion with the crosslinking agent, and obtaining a crosslinked dispersion containing a polymer p1 having a crosslinked structure and a magenta pigment. Uncrosslinked dispersion after neutralization with hydrochloric acid... 744.6 parts by mass Crosslinking agent: "Denacol EX-321" (manufactured by Nagase ChemteX Corporation) (trimethylolpropane polyglycidyl ether)... 5.4 parts by mass

[0153] Next, the crosslinked dispersion was centrifuged at 7000 G for 20 minutes in a centrifuge to remove coarse particles. The centrifuged crosslinked dispersion was filtered through a LABO-PURE filter (0.5 μm) manufactured by Loki to remove coarse particles. Furthermore, the filtered crosslinked dispersion was passed through an ultrafiltration device (crossflow ultrafilter (UF), manufactured by Sartorius) equipped with a polyethersulfone (PESU) membrane (micropore size: 0.1 μm) at a flow rate of 600 mL per minute to perform ultrafiltration. At this time, the liquid temperature was adjusted to 25°C, and ultrafiltration was performed 10 times, with one cycle being 1x the volumetric magnification of the charged liquid. Thereafter, ion-exchanged water was added so that the pigment concentration was 15% by mass, and pigment dispersion DM1 was obtained.

[0154] <Preparation of Magenta Ink> A mixture of the following composition was stirred for 60 minutes with a magnetic stirrer and then filtered through a LABO-PURE filter (0.5 μm) manufactured by Loki to obtain a magenta ink. Pigment dispersion DM1: 33.33% by mass (pigment concentration: 5% by mass), Resin particles: Particles made of styrene-butadiene copolymer, product name "Rovene 4170", manufactured by Mallard Creek Polymers... 7.5% by mass (as resin solids), DEGmEE... 3% by mass, PGmME... 10% by mass, Glycerin... 10% by mass, Water... the balance so that the total amount of the magenta ink becomes 100% by mass.

[0155] <Preparation of Cyan Ink> Cyan ink was prepared in the same manner as the magenta ink, except that the magenta pigment was changed to a cyan pigment (Pigment Blue 15:3 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.)) and the pigment concentration was changed to 4 mass %.

[0156] Examples 2 to 25, Comparative Examples 1 to 5 Uncrosslinked polymers were synthesized in the same manner as in Example 1, except that the types and contents (mass%) of the components used to synthesize the uncrosslinked polymers were changed to those shown in Table 1. Pigment dispersions were prepared in the same manner as in Example 1, except that the type of crosslinking agent was changed to those shown in Table 1. Magenta inks and cyan inks were prepared in the same manner as in Example 1, except that the types and contents (mass%) of the components contained in the inks were changed to those shown in Table 1.

[0157] Details of each component used in preparing the magenta ink are as follows:

[0158] MAA: methacrylic acid BzMA: benzyl methacrylate AA: acrylic acid BA: butyl acrylate EA: ethyl acrylate 2EHA: 2-ethylhexyl acrylate St: styrene αMe-St: α-methylstyrene MMA: methyl methacrylate C18MA: octadecyl methacrylate IBOMA: isobornyl methacrylate PDEGA: phenoxydiethylene glycol acrylate

[0159] - Crosslinking agent - Epoxy 1: "Denacol EX-321" (manufactured by Nagase ChemteX Corporation), trimethylolpropane polyglycidyl ether Epoxy 2: "Denacol EX-521" (manufactured by Nagase ChemteX Corporation), polyglycerol polyglycidyl ether Epoxy 3: "Denacol EX-861" (manufactured by Nagase ChemteX Corporation), polyethylene glycol diglycidyl ether Carbodiimide: "Carbodilite V-02" (manufactured by Nisshinbo Chemical Inc.), aqueous crosslinking agent obtained by adding a hydrophilic segment to a polycarbodiimide resin

[0160] -Resin particles- SB: Product name "Rovene 4170", manufactured by Mallard Creek Polymers, particles made of styrene butadiene copolymer PU1: Product name "Superflex 460", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., particles made of urethane resin PU2: Product name "Superflex 860", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., particles made of urethane resin PU3: Product name "Superflex E-4800", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., particles made of urethane resin

[0161] -Organic solvent- DEGmEE: diethylene glycol monoethyl ether DPGmME: dipropylene glycol monomethyl ether PGmME: propylene glycol monomethyl ether TPGmME: tripropylene glycol monomethyl ether DEGmME: diethylene glycol monomethyl ether PGmPE: propylene glycol monopropyl ether DEGmBE: diethylene glycol monobutyl ether Glycerin EG: ethylene glycol

[0162] Examples 101 to 106 Preparation of cyan ink and magenta ink An uncrosslinked polymer was synthesized in the same manner as in Example 1, except that the types and contents (mass%) of the components used to synthesize the uncrosslinked polymer were changed to those shown in Table 4. A pigment dispersion was prepared in the same manner as in Example 1, except that the type of crosslinking agent was changed to those shown in Table 4. Magenta ink and cyan ink were prepared in the same manner as in Example 1, except that the types and contents (mass%) of the components contained in the ink were changed to those shown in Table 4.

[0163] <Preparation of Overcoat Solution> Each component shown in Table 4 was stirred for 60 minutes with a magnetic stirrer and filtered through a LABO-PURE filter (0.5 μm) manufactured by Loki to obtain an overcoat solution.

[0164] Details of each component used in preparing the overcoat solution are as follows:

[0165] -Resin particles- PU1: Product name "Superflex 460", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., particles made of urethane resin PU4: Product name "Superflex 500M", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., particles made of urethane resin

[0166] - Organic solvents: Glycerin, PG: Propylene glycol, PGmME: Propylene glycol monomethyl ether

[0167] -Surfactants- Surfynol 465: acetylene glycol surfactant manufactured by Nissin Chemical Industry Co., Ltd. BYK345: silicone surfactant manufactured by BYK Corporation BYK347: silicone surfactant manufactured by BYK Corporation

[0168] -Other- ・Fabric softener: Product name: "Softer for commercial use", manufactured by Kao Corporation

[0169] Examples 201 to 204 Preparation of cyan ink and magenta ink An uncrosslinked polymer was synthesized in the same manner as in Example 1, except that the types and contents (mass%) of the components used to synthesize the uncrosslinked polymer were changed to those shown in Table 5. A pigment dispersion was prepared in the same manner as in Example 1, except that the type of crosslinker was changed to those shown in Table 5. Magenta ink and cyan ink were prepared in the same manner as in Example 1, except that the types and contents (mass%) of the components contained in the ink were changed to those shown in Table 5.

[0170] <Preparation of Pretreatment Solution> Each component shown in Table 5 was stirred for 60 minutes with a magnetic stirrer and filtered through a LABO-PURE filter (0.5 μm) manufactured by Loki to obtain a pretreatment solution.

[0171] Details of each component used in preparing the pretreatment liquid are as follows.

[0172] - Flocculant - Calcium nitrate - Cationic polymer: Product name "Catiomaster PD-7", manufactured by Yokkaichi Synthetic Co., Ltd. - Malonic acid

[0173] -Resin particles- PU4: Product name "Superflex 500M", manufactured by Daiichi Kogyo Seiyaku Co., Ltd., particles made of urethane resin

[0174] - Organic solvents PG: Propylene glycol PGmME: Propylene glycol monomethyl ether

[0175] -Surfactants- Surfynol 465: acetylene glycol surfactant manufactured by Nissin Chemical Industry Co., Ltd. Emulgen 103: polyoxyethylene lauryl ether manufactured by Kao Corporation BYK345: silicone surfactant manufactured by BYK Corporation BYK347: silicone surfactant manufactured by BYK Corporation

[0176] Examples 301 to 305 Preparation of cyan ink and magenta ink An uncrosslinked polymer was synthesized in the same manner as in Example 1, except that the types and contents (mass%) of the components used to synthesize the uncrosslinked polymer were changed to those shown in Table 6. A pigment dispersion was prepared in the same manner as in Example 1, except that the type of crosslinker was changed to those shown in Table 6. Magenta ink and cyan ink were prepared in the same manner as in Example 1, except that the types and contents (mass%) of the components contained in the ink were changed to those shown in Table 6.

[0177] <Preparation of Pretreatment Solution> Each component shown in Table 6 was stirred for 60 minutes with a magnetic stirrer and filtered through a LABO-PURE filter (0.5 μm) manufactured by Loki to obtain a pretreatment solution.

[0178] <Preparation of Overcoat Solution> Each component shown in Table 6 was stirred for 60 minutes with a magnetic stirrer and filtered through a LABO-PURE filter (0.5 μm) manufactured by Loki to obtain an overcoat solution.

[0179] [Transfer Printing] <Preparation of Image Recording Apparatus> The image recording apparatus shown in FIG. 1 was prepared. An inkjet application device was used as the pretreatment liquid application device P1. Hot air drying was used as the drying method in the pretreatment liquid drying zone DP1. An inkjet head for ejecting cyan ink was arranged as the first inkjet head IJ1, and an inkjet head for ejecting magenta ink was arranged as the second inkjet head IJ2. The ink was passed through the first drying zone D1. Hot air drying was used as the drying method in the second drying zone D2. An air-cooling zone and a hot-melt adhesive application process or an overcoat application process (not shown) were provided between the second drying zone D2 and the winding device R2. Both the first inkjet head IJ1 and the second inkjet head IJ2 were 1200 dpi (dots per inch, 1 inch = 2.54 cm) / 20-inch-wide piezo full-line heads (total number of nozzles: 2048) used. The drive frequencies of the first inkjet head IJ1 and the second inkjet head IJ2 were both set to 30 kHz.

[0180] In Examples 1 to 25, the pretreatment liquid was not applied, and the cyan ink and the magenta ink were applied in this order at an application amount per unit area of ​​6.7 g / m ２ The hot melt adhesive was applied by an ink jet recording method so that the hot melt adhesive was applied one by one.

[0181] In Examples 101 to 106, the pretreatment liquid was not applied, and the cyan ink and the magenta ink were applied in this order at an application amount per unit area of ​​6.7 g / m ２ Furthermore, the hot melt adhesive application step was not carried out, and the overcoat liquid was applied in an amount of 6.7 g / m ２ The ink was applied by an ink jet recording method so that the ink was applied to the ink layer.

[0182] In Examples 201 to 204, the amount of pretreatment liquid applied per unit area was 3.0 g / m ２ After applying the ink by the inkjet recording method so that the amount of the cyan ink and the magenta ink applied per unit area was 6.7 g / m, in this order, ２ The hot melt adhesive was applied by an ink jet recording method so that the hot melt adhesive was applied one by one.

[0183] In Examples 301 to 305, the amount of pretreatment liquid applied per unit area was 3.0 g / m ２ After applying the ink by the inkjet recording method so that the amount of the cyan ink and the magenta ink applied per unit area was 6.7 g / m, in this order, ２ Furthermore, the hot melt adhesive application step was not carried out, and the overcoat liquid was applied in an amount of 6.7 g / m ２ The ink was applied by an ink jet recording method so that the ink was applied to the ink layer.

[0184] <Image Recording> Images were recorded using the image recording device. The image recording device was loaded with a pretreatment liquid, cyan ink, and magenta ink. A DTF film (product name "DTF-H60", manufactured by Celcam Co., Ltd. (600 mm x 100 m)) was used as the impermeable substrate. First, the impermeable substrate was unwound by the unwinding device R1, and the unwound impermeable substrate was transported with tension applied. In Examples 201 to 204 and Examples 301 to 305, a pretreatment liquid was applied to the transported impermeable substrate from the pretreatment liquid application device P1. Alternatively, an OPP film (product name "Pylen Film-OT", manufactured by Toyobo Co., Ltd., thickness 25 μm) or the like can also be used as the impermeable substrate.

[0185] Next, the pretreatment liquid was dried in the pretreatment liquid drying zone DP1 using hot air at 40° C. for 3 seconds.

[0186] In Examples 1 to 25 and 101 to 106, the cyan ink was applied onto the non-permeable substrate by the first inkjet head IJ1 and passed directly through the first drying zone D1. In Examples 201 to 204 and 301 to 305, the cyan ink was applied onto the region of the non-permeable substrate where the pretreatment liquid had been applied by the first inkjet head IJ1 and passed directly through the first drying zone D1.

[0187] A magenta ink was applied by a second inkjet head IJ2 onto the area of ​​the non-permeable substrate where the cyan ink had been applied.

[0188] The magenta ink was dried in the second drying zone D2.

[0189] A multi-color image in which an image derived from magenta ink was superimposed on an image derived from cyan ink was recorded on an impermeable substrate, to obtain an image record.

[0190] The obtained image recorded material was air-cooled. In Examples 101 to 106 and 301 to 305, an overcoat liquid was applied onto the image on the image recorded material, which was then dried and wound up by winding device R2.

[0191] In Examples 1 to 25 and 201 to 204, a hot melt adhesive (product name "O-Powder", manufactured by Selcom Co., Ltd.) was applied to the image on the image-recorded material, and then heated to melt (baking). A commercially available DTF shaker, SELSHAKE-mini (manufactured by Selcom Co., Ltd.), was used to apply the hot melt adhesive, melt (baking), and wind up the image-recorded material. The image-recorded material was then unwound and cut. The cut image-recorded material and fabric were overlapped and heated and pressed together at 160°C for 2 minutes in a heat press, and the non-permeable substrate was peeled off to obtain a printed material. Note that an AF-54TEN automatic tabletop flat press (manufactured by Asahi Textile Machinery Co., Ltd.) was used for transfer.

[0192] [Evaluation] The ejection property was evaluated using cyan ink. The obtained printed textile was evaluated for washing fastness in warm water, bleeding of secondary colors, and peeling of the image due to washing and drying.

[0193] <Ejection Properties> The ejection properties were evaluated using cyan ink that had been heated at 80°C for one day immediately after preparation. The resulting image recording (one head's worth) was visually observed to check the number of streaks and ejection delays that occurred in the monochromatic image (solid image) of the image recording along the conveyance direction of the non-permeable substrate. The ejection delay was determined based on whether the ejection timing of the first ink droplet ejected from the inkjet head was delayed relative to the predetermined timing. The evaluation criteria were as follows: AA: 0 to less than 2 streaks, and no ejection delay was observed. A: 2 to less than 10 streaks, and no ejection delay was observed. B: 10 to less than 20 streaks, and no ejection delay was observed. C: 0 to less than 20 streaks, and ejection delay was observed. D: 20 or more streaks, and ejection delay was observed.

[0194] <Warm Water Washing Fastness> In the evaluation of warm water washing fastness (in the table, "Warm Water Washing Fastness"), a solid image was recorded using cyan ink, and a solid image was recorded using magenta ink. 380 g of Attack ZERO laundry detergent for drum washing (manufactured by Kao Corporation) was automatically added to a drum washing machine (product name "FLK842-W", manufactured by Iris Ohyama Co., Ltd.), and the printed fabric was washed for one cycle using the warm water 40°C course. The printed fabric was placed one by one in a laundry net and washed. After washing, the wrinkles in the printed fabric were smoothed out and it was laid flat to dry naturally. The evaluation criteria are as follows. Before and after washing in warm water, the printed fabric was measured using a fluorescence spectrodensitometer (product name "FD-7", manufactured by Konica Minolta Inc.). The color measurement results before washing were compared with the L ＊ ０ , a ＊ ０ , b ＊ ０ The color measurement results after washing in warm water are ＊ １ , a ＊ １ , b ＊ １ ΔE was calculated using the following formula: ΔE = {(L ＊ １ -L ＊ ０ ) ２ + (a ＊ １ -a ＊ ０ ) ２ +(b ＊ １ -b ＊ ０ ) １／２ A: The difference in ΔE of the printed item before and after hot water washing is 4 or less. B: The difference in ΔE of the printed item before and after hot water washing is more than 4 and not more than 8. C: The difference in ΔE of the printed item before and after hot water washing is more than 8 and not more than 12. D: The difference in ΔE of the printed item before and after hot water washing is more than 12.

[0195] <Secondary Color Bleeding> For the evaluation of secondary color bleeding (in the table, "Secondary Color Bleeding"), a character image was recorded using cyan ink, and a solid image was recorded using magenta ink. The character image was 16 pt and in MSP Gothic font "A, B, C." The character image on the printed textile was visually observed. First, it was determined whether or not the character image was distorted when magenta ink was ejected without drying after the cyan ink was ejected. If the character image was distorted, it was determined whether or not the character image was distorted when the cyan ink was ejected and then dried at 80°C for 2 seconds, and then the magenta ink was ejected. If the character image was distorted, it was determined whether or not the character image was distorted when the cyan ink was ejected and then dried at 80°C for 4 seconds, and then the magenta ink was ejected. If the character image was distorted, it was determined whether or not the character image was distorted when the cyan ink was ejected and then dried at 80°C for 8 seconds, and then the magenta ink was ejected. If there was no blurring of the character images, the test was terminated at that point. The evaluation criteria were as follows: AA: There was no blurring of the character images even though the cyan ink was not dried after being ejected. A: There was no blurring of the character images after the cyan ink was ejected and dried for 2 seconds. B: There was no blurring of the character images after the cyan ink was ejected and dried for 4 seconds. C: There was no blurring of the character images after the cyan ink was ejected and dried for 8 seconds. D: There was blurring of the character images after the cyan ink was ejected and dried for 8 seconds.

[0196] <Image Peeling Due to Washing and Drying> To evaluate image peeling due to washing and drying (in the table, "Drying Image Peeling"), a solid image was recorded using cyan ink, and a solid image was recorded using magenta ink. 380 g of Attack ZERO laundry detergent (manufactured by Kao Corporation) for drum-type washing machines (product name "FLK842-W", manufactured by Iris Ohyama Co., Ltd.) was automatically loaded into a drum-type washing machine, and the printed fabrics were washed in two cycles using a hot water 40°C course. The printed fabrics were placed one by one in a laundry net and washed. After washing, the fabrics were tumble dried in the automatic drying mode. After drying, the presence or absence of image peeling was visually confirmed. If image peeling was not confirmed, the test was terminated. If image peeling was confirmed, the same operations as above were performed except that the printed fabrics were washed in one cycle using a hot water 40°C course, and then the presence or absence of image peeling was confirmed. The evaluation criteria are as follows. A: No peeling of the image was observed after two cycles of hot water washing and tumble drying. B: No peeling of the image was observed after one cycle of hot water washing and tumble drying. C: Peeling of the image of 1 mm or less in width was observed after one cycle of hot water washing and tumble drying. D: Peeling of the image of more than 1 mm in width was observed on the printed matter after one cycle of hot water washing and tumble drying.

[0197] The evaluation results are shown in Tables 1 to 6. In Tables 1 to 6, the type and content (mass%) of the polymerizable monomer used in synthesizing the crosslinked polymer contained in the ink are shown. The proportion (mass%) of hydrophobic monomer means the proportion of the hydrophobic monomer in the polymerizable monomer used in synthesizing the crosslinked polymer. T Ｄ means the glass transition temperature of the crosslinked polymer. Ｌ indicates the glass transition temperature of the resin particles. The type and number of functional groups of the crosslinking agent used in synthesizing the crosslinked polymer are also listed. In Comparative Examples 1 to 3 and 5, no crosslinking agent was used, so "-" is listed in the crosslinking agent column.

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204] As shown in Tables 1 to 3, Examples 1 to 25 contain water, pigment, crosslinked polymer, and resin particles, and the resin particle content is 5% by mass or more, resulting in excellent jetting properties. Furthermore, when printed materials are used, the prints exhibit excellent fastness to washing in warm water, and image peeling due to washing and drying is suppressed. On the other hand, Comparative Example 1 does not contain a crosslinked polymer and the resin particle content is less than 5% by mass, resulting in all evaluation results being D. Comparative Example 2 does not contain a crosslinked polymer, resulting in poor jetting properties and poor fastness to washing in warm water, and image peeling due to drying is observed. Comparative Example 3 does not contain a crosslinked polymer, resulting in poor jetting properties and image peeling due to drying. Comparative Example 4 contains less than 5% by mass of resin particles, resulting in poor fastness to washing in warm water. Comparative Example 5 does not contain a crosslinked polymer, resulting in slightly poor jetting properties and image peeling due to drying.

[0205] In Example 25, an organic solvent having an SP value of 26 or less was further contained, and the content of the organic solvent having an SP value of 26 or less was 3 mass% or more, and it was found that bleeding of the secondary color was suppressed compared to Example 24.

[0206] In Examples 2 and 3, the crosslinked polymer was crosslinked with an epoxy compound, and it was found that, compared with Example 4, peeling of the image due to drying was suppressed.

[0207] In Example 11, the glass transition temperature T Ｄ It was found that the temperature was 50° C. or higher, and compared with Example 12, the fastness to washing in warm water was excellent and peeling of the image due to drying was suppressed.

[0208] In Example 13, the glass transition temperature T Ｌ It was found that, compared with Example 17, the image had excellent fastness to washing in warm water and image peeling due to drying was suppressed.

[0209] In Example 12, "T Ｄ -T Ｌ " was 50°C or higher, and it was found that the fastness to washing in hot water was superior to that of Example 17. Ｄ -T Ｌ " was 160°C or less, and compared with Example 18, it was found that the ejection property was excellent, the fastness to washing in warm water was excellent, and peeling of the image due to drying was suppressed.

[0210] Furthermore, it was found that bleeding of the secondary color was significantly suppressed when the pretreatment liquid was used, as shown in Table 5. Furthermore, it was found that transfer printing could be performed without applying a hot melt adhesive when the overcoat liquid was used.

[0211] It was also found that similar evaluation results were obtained when a commercially available crosslinked dispersion (product name "APD1000 Magenta", manufactured by Fujifilm Imaging Colorants) was used instead of the pigment dispersion DM1 in Example 1. Furthermore, in Example 301, the overcoat liquid was applied using an anilox roller at an amount of 6.7 g / m per unit area. ２ It was found that similar evaluation results were obtained even when the values ​​were assigned as follows:

[0212] The disclosure of Japanese Patent Application No. 2024-048727, filed on March 25, 2024, is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. A transfer printing ink comprising water, a pigment, a polymer having a crosslinked structure, and resin particles, wherein the content of the resin particles is 5% by mass or more relative to the total amount of the transfer printing ink.

2. The transfer printing ink according to claim 1, further comprising an organic solvent having an SP value of 26 or less, wherein the content of said organic solvent having an SP value of 26 or less is 3 mass% or more relative to the total amount of the transfer printing ink.

3. The transfer printing ink according to claim 1, wherein the polymer having a crosslinked structure is crosslinked with an epoxy compound.

4. The glass transition temperature T of the polymer having the crosslinked structure Ｄ The transfer printing ink according to claim 1, wherein the temperature is 50° C. or higher.

5. The glass transition temperature T of the resin particles Ｌ The transfer printing ink according to claim 1, wherein the temperature of the ink is 30° C. or lower.

6. The glass transition temperature T of the polymer having the crosslinked structure Ｄ and the glass transition temperature T Ｌ The transfer printing ink according to claim 1, which satisfies the following formula (1): 50°C≦T Ｄ -T Ｌ ≦160° C. ... (1) 7. The transfer printing ink according to claim 2, wherein the organic solvent having an SP value of 26 or less is an alkylene glycol alkyl ether.

8. The transfer printing ink according to claim 1, wherein the polymer having a crosslinked structure is a crosslinked polymer in which the content of structural units derived from polymerizable monomers having at least one hydrophobic group selected from the group consisting of alkyl groups having 10 or more carbon atoms and aromatic hydrocarbon groups is 50% by mass or more.

9. A transfer printing ink set comprising: a transfer printing ink containing water, a pigment, a polymer having a crosslinked structure, and resin particles, wherein the content of the resin particles is 5 mass% or more relative to the total amount of the transfer printing ink; and an overcoat liquid containing the resin particles.

10. The transfer printing ink set according to claim 9, wherein the content of the resin particles in the overcoat liquid is 7% by mass or more relative to the total amount of the overcoat liquid.

11. The transfer printing ink set according to claim 9, wherein the overcoat liquid contains a cationic surfactant.

12. A transfer printing ink set comprising the transfer printing ink according to any one of claims 1 to 8 and a pretreatment liquid containing a flocculant.

13. A transfer printing ink set comprising: the transfer printing ink according to any one of claims 1 to 8; an overcoat liquid for transfer printing containing resin particles; and a pretreatment liquid containing a flocculant.

14. A transfer printing method comprising the steps of: applying the transfer printing ink according to any one of claims 1 to 8 onto an impermeable substrate to record an image; and transferring the image recorded on the impermeable substrate to a fabric.

Images