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

Abstract

An ink for transfer printing and use thereof, the ink for transfer printing containing water, a pigment, a polymer having a crosslinked structure, and resin particles, the content of the resin particles being 5% by mass or more relative to the total amount of the ink for transfer printing.

Description

Technical Field

[0001] This invention relates to a transfer printing ink, a set of transfer printing inks, and a transfer printing method. Background Technology

[0002] In recent years, various studies have been conducted on the printing and dyeing methods of fabrics. For example, Japanese Patent Application Publication No. 2023-87372 discloses a printing method that depicts an image printed on a transfer medium onto a transfer medium by transferring the image onto the transfer medium. The printing method is characterized by comprising: a printing stage in which an image is printed on the transfer medium using a printing apparatus that performs printing by inkjet printing; a hot melt resin adhesion stage in which hot melt resin powder, which is a powder containing resin softened by heating, is adhered to the transfer medium on which the image is printed; and a transfer stage in which the transfer medium with the adhered hot melt resin powder is subjected to a process... Heat causes the resin portion, formed from the softened hot-melt resin powder, to adhere to the transfer medium, thereby transferring the image from the transfer medium to the transfer medium. The printing apparatus includes: a colored ink printhead that ejects colored ink as ink containing pigments representing colored colors; and a transparent ink printhead that ejects transparent ink as colorless and translucent ink. During the printing stage, transparent ink is further ejected from the transparent ink printhead for at least a portion of the area on the transfer medium from which the colored ink is ejected from the colored ink printhead. Summary of the Invention The technical problem to be solved by the invention

[0003] In transfer printing and dyeing, it is sometimes required to improve the ink ejectibility, ensure excellent wash fastness of the printed material under warm water conditions, and suppress image peeling caused by washing and drying.

[0004] The present invention was made in view of this situation. The problem to be solved by the embodiments of the present invention is to provide a transfer printing ink, a transfer printing ink group and a transfer printing method, which can obtain a printed product with excellent sprayability, excellent wash fastness under warm water conditions and suppressed image peeling caused by washing and drying. means for solving technical problems

[0005] The present invention includes the following methods. <1> A transfer printing ink contains water, pigments, a cross-linked polymer, and resin particles. The content of resin particles is more than 5% by mass relative to the total amount of ink used for transfer printing and dyeing. <2> The transfer printing ink described in <1> also contains organic solvents with an SP value of 26 or less. The content of organic solvents with an SP value of 26 or less is more than 3% by mass relative to the total amount of ink used for transfer printing and dyeing. <3> According to the transfer printing ink described in <1> or <2>, wherein, Organic solvents with an SP value below 26 are alkylene glycol alkyl ethers. <4> The transfer printing ink according to any one of <1> to <3>, wherein, Polymers with cross-linked structures are cross-linked by epoxy compounds. <5> The transfer printing ink according to any one of <1> to <4>, wherein, Glass transition temperature T of polymers with cross-linked structures D Temperatures above 50°C. <6> The transfer printing ink according to any one of <1> to <5>, wherein, Glass transition temperature T of resin particles L The temperature is below 30℃. <7> The transfer printing ink according to any one of <1> to <6>, wherein, Glass transition temperature T of polymers with cross-linked structures D and the glass transition temperature T of resin particles L It satisfies the following equation (1). 50℃≤T D -T L ≤160℃…(1) <8> The transfer printing ink according to any one of <1> to <7>, wherein, The polymer having a cross-linked structure is a cross-linked polymer, wherein the content of structural units derived from polymeric monomers having at least one hydrophobic group selected from the group consisting of alkyl and aromatic hydrocarbon groups with more than 10 carbon atoms is 50% by mass or more. <9> A transfer printing ink set, comprising: The transfer printing ink contains water, pigments, cross-linked polymers, and resin particles, wherein the content of resin particles is 5% by mass or more relative to the total amount of the transfer printing ink; and External coating liquid containing resin particles. <10> According to the transfer printing ink set described in <9>, wherein... The resin particle content in the external coating liquid is more than 7% by mass relative to the total amount of the external coating liquid. <11> According to the transfer printing ink set described in <9> or <10>, wherein, The topical coating contains softener. <12> A transfer printing ink set, comprising: Transfer printing inks as described in any one of <1> to <8>; and The pretreatment solution contains a coagulant. <13> A transfer printing ink set, comprising: Transfer printing inks as described in any one of <1> to <8>; The external coating solution for transfer printing and dyeing contains resin particles; and The pretreatment solution contains a coagulant. <14> A transfer printing method includes the following steps: To record an image by applying any one of <1> to <8> of the transfer printing ink onto a non-permeable substrate; and The image recorded on a non-permeable substrate is transferred onto the fabric. Invention Effects

[0006] According to the present invention, a transfer printing ink, a set of transfer printing inks, and a transfer printing method can be provided, which can obtain printed materials with excellent sprayability, excellent wash fastness under warm water conditions, and suppressed image peeling caused by washing and drying. Attached Figure Description

[0007] Figure 1 This is a conceptual illustration of the image recording apparatus used in the embodiments. Detailed Implementation

[0008] The following is a detailed description of the transfer printing ink, the transfer printing ink set, and the transfer printing method of the present invention.

[0009] In this specification, the numerical range represented by “~” indicates the range that includes the minimum and maximum values ​​recorded before and after “~”, respectively. In the numerical ranges described in this specification, the upper or lower limit of a certain numerical range can be replaced with the upper or lower limit of other numerical ranges described in different stages. Furthermore, within the numerical ranges described in this specification, the upper or lower limit of a certain numerical range can also be replaced with the values ​​shown in the embodiments.

[0010] In this specification, when multiple substances corresponding to each component are present in the composition, unless otherwise stated, the amount of each component in the composition refers to the total amount of the multiple substances present in the composition. In this specification, a combination of two or more preferred methods is a more preferred method. In this specification, the term "process" includes not only independent processes, but also processes that can not be clearly distinguished from other processes, as long as the intended purpose of the process can be achieved.

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

[0012] If an image is recorded using the ink of the present invention and then transferred onto fabric, a printed product with excellent wash fastness under warm water conditions and suppressed image peeling due to washing and drying can be obtained. Furthermore, the ink of the present invention exhibits excellent ejectibility.

[0013] The reason is still unclear, but the following is a speculation.

[0014] The ink of the present invention contains a polymer with a cross-linked structure, thus the polymer with the cross-linked structure functions as a dispersant for dispersing pigments. The polymer with the cross-linked structure exhibits excellent adsorption properties for pigments, therefore the ink of the present invention has excellent sprayability. Furthermore, the ink of the present invention contains a polymer with a cross-linked structure, and the resin particle content is 5% by mass or more, thus improving the adhesion of the image to fabric, suppressing image peeling caused by washing and drying, and exhibiting excellent wash fastness under warm water conditions. In particular, it is known that the tensile strength of the ink film is improved by incorporating a polymer with a cross-linked structure. The high tensile strength of the ink film suppresses image breakage due to the deformation of the fabric caused by external force applied during warm water washing and drying. Consequently, image peeling is considered to be suppressed.

[0015] In contrast, Japanese Patent Application Publication No. 2023-87372 does not contain any information related to the determination of polymers with cross-linked structures, resin particles and their content ratios.

[0016] The components contained in the ink of the present invention will be described below.

[0017] <Water> The ink contains water. The water content relative to the total amount of ink 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. The upper limit of the water content relative to the total amount of ink is appropriately determined based on the content of other components, for example, 99% by mass, preferably 95% by mass, and more preferably 90% by mass.

[0018] <Pigment> The ink of this invention contains pigments.

[0019] The pigment can be either a commercially available organic pigment or an inorganic pigment. As for pigments, examples include those described in Seishiro Itō's "Encyclopedia of Pigments" (2000), W. Herbst and K. Hunger's "Industrial Organic Pigments", Japanese Patent Application Publication Nos. 2002-12607, 2002-188025, 2003-26978, and 2003-342503.

[0020] Furthermore, the pigment can be a water-insoluble pigment that can be dispersed in water by a dispersant, or it can be a self-dispersing pigment. Self-dispersible pigments are pigments that can be dispersed in water even without the use of a dispersant. Self-dispersible pigments refer to compounds formed by direct or chemical bonding to the surface of a pigment via other groups, for example, at least one of the following groups selected from the group consisting of hydrophilic groups such as carbonyl, hydroxyl, carboxyl, sulfonyl, phosphate and their salts.

[0021] Pigments can be colored pigments (e.g., cyan, magenta, yellow, etc.) or achromatic pigments (e.g., white and black).

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

[0023] <Polymers with cross-linked structures> The ink of the present invention contains a polymer having a cross-linked structure. There are no particular limitations on polymers with cross-linked structures, as long as they have at least one cross-linked structure within the molecule. Polymers with cross-linked structures preferably function as dispersants for dispersing pigments contained in the inks of the present invention.

[0024] Whether the polymer contained in the ink has a cross-linked structure can be determined, for example, by the following methods. First, the polymer in the ink is separated using separation methods such as solvent extraction. Then, the separated polymer is analyzed using various analytical methods such as nuclear magnetic resonance (NMR), infrared spectroscopy (IR), and thermal analysis to comprehensively determine whether a cross-linked structure exists.

[0025] A polymer having a cross-linked structure (hereinafter referred to as a "cross-linked polymer") is, for example, a cross-linked polymer formed by cross-linking an uncross-linked polymer using a cross-linking agent. The uncross-linked polymer is preferably a water-soluble polymer.

[0026] In this invention, "water-soluble" in "water-soluble polymer" refers to the property that the amount of the polymer that can be dissolved in 100g of distilled water at 25°C is 2g or more. Preferably, the amount of the water-soluble polymer that can be dissolved in distilled water at 25°C is 5g or more, more preferably 10g or more.

[0027] The uncrosslinked polymer is preferably a polymer having functional groups that can be crosslinked using a crosslinking agent. Examples of crosslinkable functional groups include carboxyl groups or their salts, isocyanate groups, and epoxy groups. From the viewpoint of improving pigment dispersibility, the crosslinkable functional group is preferably a carboxyl group or its salt, and particularly preferably a carboxyl group. That is, the uncrosslinked polymer is preferably a polymer containing a carboxyl group.

[0028] The uncrosslinked polymer is preferably a copolymer containing structural units derived from a carboxyl-containing polymeric monomer (hereinafter referred to as "carboxyl-containing monomer"). The copolymer may contain only one type of structural unit derived from the carboxyl-containing monomer or more than one type. The copolymer may be a random copolymer or a block copolymer, but a random copolymer is preferred.

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

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

[0031] The uncrosslinked polymer preferably contains structural units derived from polymeric monomers having hydrophobic groups (hereinafter also referred to as "hydrophobic monomers") in addition to structural units derived from carboxyl-containing monomers. The copolymer may contain only one type of structural unit derived from hydrophobic monomers or more than two types.

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

[0033] The polymerizable groups contained in the hydrophobic monomer are preferably olefinic unsaturated groups, more preferably vinyl, allyl or (meth)acryloyl, and even more preferably (meth)acryloyl.

[0034] From the viewpoint of pigment adsorption, the uncrosslinked polymer is preferably a polymer in which the content of structural units derived from hydrophobic monomers is 50% by mass or more. More preferably, the content of structural units derived from hydrophobic monomers in the uncrosslinked polymer is 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, more preferably 10 to 18.

[0036] In monomers containing alkyl groups having 10 or more carbon atoms, the alkyl group can be a straight-chain alkyl group, a branched alkyl group, or a cyclic alkyl group. From the viewpoint of pigment adsorption, a straight-chain alkyl group is preferred.

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

[0038] Examples of aromatic hydrocarbon groups in monomers include, for example, phenyl and naphthyl groups. Examples of monomers having aromatic hydrocarbon groups 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 structural units derived from carboxyl-containing monomers and structural units derived from hydrophobic monomers, more preferably a random copolymer containing structural units derived from (meth)acrylic acid and structural units derived from hydrophobic monomers, and particularly preferably a random copolymer containing structural units derived from (meth)acrylic acid and structural units derived from benzyl (meth)acrylate.

[0040] From the viewpoint of pigment dispersibility, the acid value of the uncrosslinked polymer is preferably 65 mg KOH / g to 220 mg KOH / g, and more preferably 65 mg KOH / g to 170 mg KOH / g.

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

[0042] There is no particular limitation on the weight-average molecular weight (Mw) of the uncrosslinked polymer, 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 weight-average molecular weight for cross-linked polymers is the same as that for uncross-linked polymers.

[0044] In this invention, the weight-average molecular weight was determined using gel permeation chromatography (GPC). For example, an HLC-8220 GPC (manufactured by TOSOH CORPORATION) was used as the GPC column, three TSKgel Super Multipore HZ-H (manufactured by TOSOH CORPORATION, 4.6 mm ID × 15 cm) were used as the eluent, and THF (tetrahydrofuran) was used. The conditions were set as follows: sample concentration 0.45% by mass, flow rate 0.35 ml / min, sample injection volume 10 μL, measurement temperature 40°C, and detection using a differential refractive index (RI) detector. Calibration curves were prepared using eight samples manufactured by Tosoh Corporation under the product name "TSK Standard Polystyrene": "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", "A-1000", and "n-propylbenzene" as standard samples.

[0045] When crosslinking an uncrosslinked polymer, the crosslinking agent used is preferably a compound having two or more reaction sites with the uncrosslinked polymer (e.g., a polymer with carboxyl groups). Only one crosslinking agent may be used, or two or more may be used.

[0046] From a reactivity point of view, the crosslinking agent is preferably an epoxy compound. That is, the cross-linked polymer is preferably cross-linked by an epoxy compound.

[0047] The cross-linking of polymers by epoxy compounds can be confirmed by acid value determination and 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., an epoxy compound with two or more functional groups) and a polymer having carboxyl groups. In this combination, a crosslinked structure is formed by the reaction of epoxy groups and carboxyl groups. The formation of the crosslinked structure using the crosslinking agent is preferably carried out after dispersing the pigment using the uncrosslinked polymer.

[0049] Examples of epoxy compounds with two or more functions 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 them, the epoxy compound with two or more functions is preferably polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, or trimethylolpropane triglycidyl ether.

[0051] Crosslinking agents can be commercially available products. Commercially available products include, for example, Denacol EX-321, EX-521, EX-821, EX-830, EX-850, EX-851 and EX-861 (manufactured by Nagase ChemteX Corporation).

[0052] From the viewpoint of crosslinking reaction rate and dispersion stability after crosslinking, the molar ratio of the reactive site (e.g., epoxy group) in the crosslinking agent to the reactive site (e.g., carboxyl 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.

[0053] From the perspective of improving wash fastness under warm water conditions and further suppressing image peeling caused by washing and drying, the glass transition temperature T of the crosslinked polymer is... D Preferably, the temperature is 50°C or higher, more preferably 70°C or higher. Glass transition temperature T DThe upper limit is, for example, 140℃.

[0054] In this invention, the glass transition temperature is determined using a differential scanning calorimeter, for example, using the product name "DSC-60" manufactured by SHIMADZUCORPORATION.

[0055] <Resin Particles> The ink of this invention contains resin particles. Here, resin particles are particles composed of resin, which distinguishes them from the polymers with cross-linked structures mentioned above.

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

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

[0058] The preferred resin particles are those made of acrylic resin, styrene-acrylic resin, polyester, polyurethane resin, styrene-butadiene copolymer, or polyolefin resin.

[0059] Self-dispersible resin particles are preferred as resin particles. Examples of self-dispersible resin particles include those described in Japanese Patent Application Publication No. 2016-188345, paragraphs 0062 to 0076, and International Publication No. 2013 / 180074, paragraphs 0109 to 0140.

[0060] The molecular weight of the resin in the resin particles, measured by weight-average molecular weight, is preferably 10 million to 300,000, more preferably 20 million to 200,000, and even more preferably 50 million to 100,000.

[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 this invention, the volume average particle size is represented by the value measured by a laser diffraction / scattering particle size analyzer. As a measuring device, for example, the particle size distribution measuring device “Microtrac MT-3300II” (manufactured by Nikkiso Co., Ltd.) can be cited.

[0063] The content of resin particles relative to the total amount of ink is 5% by mass or more, preferably 7% by mass or more. If the resin particle content is 5% by mass or more, the abrasion resistance is excellent. From the viewpoint of spray stability, the content of 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 polymers D and the glass transition temperature T of resin particles L Preferably, the following equation (1) is satisfied. 50℃≤T D -T L ≤160℃…(1)

[0065] If "T" D -T L "If the temperature is above 50°C, the glass transition temperature of the cross-linked polymer is relatively high, which can improve the fracture strength. On the other hand, the glass transition temperature of the resin particles is relatively low, which results in excellent film-forming properties. Through the synergistic effect of the two, good wash fastness can be achieved." If "T" D -T L "If the temperature is below 160°C, image peeling caused by washing and drying can be further suppressed."

[0066] “T D -T L "More preferably, it is 70℃~110℃."

[0067] <Organic solvents with an SP value below 26> The ink of the present invention preferably contains an organic solvent with an SP value of 26 or less (hereinafter also referred to as "organic solvent A").

[0068] In this invention, the SP value refers to a value expressed as the square root of the intermolecular cohesive energy (solution parameter), and is a value calculated using the method described in RFFedors, Polymer Engineering Science, 14, pp. 147-154 (1974). In this invention, the unit for the SP value is MPa. 1 / 2 .

[0069] The following examples illustrate organic solvents and their SP values. The values ​​in parentheses represent the SP values. 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 ) Isopropanol (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 tert-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 formed ink film, organic solvent A is preferably an alkylene glycol alkyl ether, more preferably a diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether or tripropylene glycol monoalkyl ether.

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

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

[0073] Depending on the requirements, the ink of the present invention may contain additives such as surfactants, co-sensitizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, and alkaline compounds.

[0074] [Transfer Printing Inks] The first aspect of the transfer printing ink group (hereinafter also referred to as the "ink group") of the present invention includes the ink of the present invention and an external coating liquid containing resin particles.

[0075] The second embodiment of the ink group of the present invention includes the ink of the present invention and a pretreatment liquid containing a coagulant.

[0076] The third embodiment of the ink group of the present invention includes the ink of the present invention, a transfer printing and dyeing external coating liquid containing resin particles, and a pretreatment liquid containing a coagulant.

[0077] The details of the inks in the first, second, and third embodiments of the ink group of the present invention are as described above.

[0078] <Method 1> The pretreatment solution contains at least one coagulant.

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

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

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

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

[0083] Preferably, at least a portion of the polyvalent metal compound dissociates into polyvalent metal ions and counterions in the pretreatment solution.

[0084] -Organic acids- Organic acids can be exemplified by organic compounds that have acidic groups.

[0085] Examples of acidic groups include phosphate, phosphonic acid, hypophosphonic acid, sulfate, sulfonic acid, sulfinic acid, and carboxyl groups.

[0086] From the perspective of ink coagulation speed, the acidic group is preferably a phosphate group or a carboxyl group, and more preferably a carboxyl group.

[0087] Preferably, at least a portion of the acidic groups dissociate in the pretreatment solution.

[0088] Examples of organic compounds containing a carboxyl group include (meth)acrylic acid, poly(meth)acrylic acid, acetic acid, formic acid, benzoic acid, ethylene glycol, 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, pyrrolidone carboxylic acid, pyranone carboxylic acid, pyrrolic carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, and nicotinic acid.

[0089] From the viewpoint of ink agglomeration speed, organic compounds with carboxyl groups are preferably carboxylic acids with a valence of 2 or higher (hereinafter also referred to as polycarboxylic acids), and more preferably dicarboxylic acids.

[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 pKa of the organic acid is preferably low (e.g., 1.0 to 5.0). This reduces the surface charge of pigments, resin particles, and other particles in the ink, which are dispersed and stabilized by weakly acidic functional groups such as carboxyl groups, by bringing them into contact with the organic acid, which has a lower pKa, thereby reducing the dispersion stability.

[0092] The organic acid is preferably low in pKa, highly soluble in water, and has a valence of 2 or higher. Furthermore, the organic acid is more preferably high in the pH region where it has a lower pKa than the functional group (e.g., carboxyl group) used to stabilize particle dispersion in the ink.

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

[0094] The metal complex is preferably a metal complex containing at least one ligand selected from the group consisting of acetate, acetylacetonate, methyl acetoacetate, ethyl acetoacetate, octanediol, butoxyacetylacetonate, lactate, ammonium lactate and triethanolamine.

[0095] Metal complexes are commercially available. Various organic ligands, especially multidentate ligands capable of forming metal chelating catalysts, are commercially available. Therefore, metal complexes can be prepared by combining commercially available organic ligands with metals.

[0096] Examples of metal complexes include zirconium tetraacetylacetone (e.g., ORGATIX ZC-150 manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium monoacetylacetone (e.g., ORGATIX ZC-540 manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium diacetylacetone (e.g., ORGATIX ZC-550 manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium monoacetoacetate (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.), diisopropoxybis(acetylacetone)titanium (e.g., ORGATIX TC-100 manufactured by Matsumoto Fine Chemical Co., Ltd.), and titanium tetraacetylacetone (e.g., ORGATIX manufactured by Matsumoto Fine Chemical Co., Ltd.). TC-401”), dioctyloxybis(octyl glycol) titanium (e.g., “ORGATIX TC-200” manufactured by Matsumoto Fine Chemical Co., Ltd.), diisopropoxybis(ethyl acetoacetate) titanium (e.g., “ORGATIX TC-750” manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium tetraacetylacetonate (e.g., “ORGATIX ZC-700” manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium tributoxymonoacetylacetonate (e.g., “ORGATIX ZC-540” manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium monobutoxyacetylacetonate bis(ethyl acetoacetate) (e.g., “ORGATIX ZC-570” manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium dibutoxybis(ethyl acetoacetate) (e.g., “ORGATIX ZC-580” manufactured by Matsumoto Fine Chemical Co., Ltd.), aluminum triacetylacetonate (e.g., “ORGATIX ZC-580” manufactured by Matsumoto Fine Chemical Co., Ltd.), etc. ORGATIX AL-80 (manufactured by Co., Ltd.), titanium ammonium lactate (e.g., Matsumoto Fine Chemical Co., Ltd.).This includes compounds such as "ORGATIX TC-300", titanium lactate (e.g., "ORGATIX TC-310, 315" manufactured by Matsumoto Fine Chemical Co., Ltd.), titanium triethanolamine ("ORGATIX TC-400" manufactured by Matsumoto Fine Chemical Co., Ltd.), and zirconium chloride compounds (e.g., "ORGATIX ZC-126" manufactured by Matsumoto Fine Chemical Co., Ltd.).

[0097] The metal complex is preferably titanium ammonium lactate (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 zirconium chloride compound (e.g., ORGATIX ZC-126 manufactured by Matsumoto Fine Chemical Co., Ltd.).

[0098] -Catonic polymer- Furthermore, the pretreatment solution can be in the form of a coagulating component containing one or more cationic polymers. The cationic polymers are preferably homopolymers, copolymers, or condensation polymers of cationic monomers having primary to tertiary amino groups or quaternary ammonium groups. As cationic polymers, they can be used in any form, either as water-soluble polymers or water-dispersible latex particles. Examples of cationic polymers include, for example, polyvinylpyridine salts, polyalkylaminoethyl acrylates, polyalkylaminoethyl methacrylates, polyvinylimazoles, polyethyleneimine, polybiguanidines, polyguanidines, polyallylamines, and their derivatives.

[0099] From the viewpoint of the viscosity of the pretreatment solution, a lower weight-average molecular weight is preferable for cationic polymers. When the pretreatment solution is applied to the recording medium using an inkjet printing method, a weight-average molecular weight of 1,000 to 500,000 is preferred, 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 higher is advantageous from the viewpoint of coagulation rate. A weight-average molecular weight of 500,000 or lower is advantageous in terms of ejection reliability. However, this is not a limitation when the pretreatment solution is applied to the recording medium by methods other than inkjet printing.

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

[0101] Depending on the requirements, the pretreatment solution may contain other components besides coagulants. Other components that may be contained in the pretreatment solution include organic solvents, resin particles, surfactants, solid wetting agents, colloidal silica, inorganic salts, anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, mildew inhibitors, pH adjusters, viscosity adjusters, rust inhibitors, chelating agents, and water-soluble polymers (e.g., the water-soluble polymers described in paragraphs 0026 to 0080 of Japanese Patent Application Publication No. 2013-001854).

[0102] <Method 2> The external coating liquid contains at least one type of resin particles.

[0103] Examples of resin particles contained in the coating liquid include resin particles identical to those contained in ink. From the viewpoint of image transferability and adhesion to the substrate, the resin particles contained in the coating liquid are preferably particles composed of urethane resin or styrene-acrylic resin.

[0104] From the viewpoint of image transferability and adhesion to the substrate, the content of resin particles relative to the total amount of the topcoat liquid is preferably 7% by mass or more, and more preferably 10% by mass or more. From the perspective of ejection properties, the upper limit of the resin particle content is, for example, 20% by mass.

[0105] The external coating solution preferably contains a cationic surfactant. Commercially available fabric softeners (specifically, fabric softeners) typically contain cationic surfactants. Therefore, it is preferable to use fabric softeners containing cationic surfactants by adding them to the coating liquid.

[0106] If the coating contains cationic surfactants, the fabric will feel softer due to the cationic surfactants contained in the softener. As a cationic surfactant, it is not particularly limited, and conventionally known cationic surfactants can be used. Examples of cationic surfactants include alkylamine salts, quaternary ammonium salts, alkyl imidazoline onion salts, polyoxyethylene alkylamine salts, and polyvinyl polyamine derivatives.

[0107] (Other ingredients) The coating liquid may contain other components besides resin particles and softeners as needed. Other components that may be contained in the coating liquid include organic solvents, surfactants, solid wetting agents, colloidal silica, inorganic salts, anti-fading agents, emulsion stabilizers, penetration promoters, ultraviolet absorbers, preservatives, mildew inhibitors, pH adjusters, viscosity adjusters, rust inhibitors, chelating agents, and water-soluble polymers (e.g., the water-soluble polymers described in paragraphs 0026 to 0080 of Japanese Patent Application Publication No. 2013-001854).

[0108] <Third Method> The preferred methods for the pretreatment liquid and the external coating liquid in the third method are the same as the preferred methods for the pretreatment liquid in the first method and the preferred methods for the external coating liquid in the second method.

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

[0110] <Ink Application Process> The transfer printing method of the present invention includes a step of applying the ink of the present invention to a non-permeable substrate to record an image.

[0111] In this invention, the non-permeability of the non-permeable substrate refers to its property of having a water absorption rate of 2.5% or less over 24 hours, as measured according to ASTM D570-98 (2018). Here, "%" as the unit of water absorption rate is a mass standard. The aforementioned water absorption rate is preferably 1.0% or less, more preferably 0.5% or less.

[0112] Materials that can be used as non-permeable substrates include, for example, 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 non-permeable substrate is preferably made of resin. That is, the non-permeable substrate is preferably a resin substrate.

[0114] From a general perspective, the preferred materials for non-permeable substrates are polypropylene, polyethylene, polyethylene terephthalate, nylon, acrylic resin, or polyvinyl chloride.

[0115] The shape of the non-permeable substrate is preferably sheet (film) or plate. Examples of non-permeable substrates with this shape include glass plates, metal plates, resin sheets (resin films), paper laminated with plastic, paper laminated or deposited with metal, and plastic sheets (plastic films) laminated or deposited with metal.

[0116] As a resin-based non-permeable substrate, resin sheets (resin films) can be cited as an example. In particular, commercially available resin sheets for DTF printing are preferred, specifically, DTF-H60 (manufactured by SELCAM Co., Ltd.) and the like can be used.

[0117] The thickness of the non-permeable 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] Hydrophilication treatment can also be applied to non-permeable substrates. Examples of hydrophilication treatments include corona treatment, plasma treatment, flame treatment, heat treatment, abrasion treatment, light irradiation treatment (e.g., UV treatment), and flame treatment, but are not limited to these. Corona treatment can be performed, for example, using a corona treatment machine (product name "PS-10S", manufactured by Shinko Electric & Instrumentation Co., Ltd.). The conditions for corona treatment can be appropriately selected based on the type of non-permeable substrate.

[0119] <Application of Ink> The application of ink can be carried out using known application methods such as coating, inkjet recording, and immersion.

[0120] As a coating method, known coating methods include those using bar coaters, die coaters, air knife coaters, blade coaters, bar coaters, knife coaters, extrusion coaters, and reverse roller coaters.

[0121] There are no particular restrictions on the way ink is ejected in inkjet recording. It can be any of the known methods, such as charge control method that uses electrostatic attraction to eject ink, on-demand inkjet method (pressure pulse method) that uses the vibration pressure of piezoelectric elements, acoustic inkjet method that converts electrical signals into sound beams that irradiate the ink and uses radiation pressure to eject ink, and thermal inkjet method (Bubble Jet (registered trademark)) that heats the ink to form bubbles and uses the resulting pressure.

[0122] As an inkjet recording method, the following inkjet recording method can be used particularly effectively: by means of the method described in Japanese Patent Application Publication No. 54-59936, ink subjected to heat energy undergoes a rapid volume change, and ink is ejected from the nozzle by force based on this state change. The method described in paragraphs 0093 to 0105 of Japanese Patent Application Publication No. 2003-306623 can also be used as an inkjet recording method.

[0123] Applying ink to a non-permeable substrate using inkjet recording is done by ejecting ink from the nozzles of an inkjet head.

[0124] As for inkjet head types, there are shuttle methods that record while scanning along the width of the recording medium using a short serial head; and line methods that use a line head that arranges recording elements corresponding to the entire area of ​​one side of the recording medium.

[0125] In the inline method, the recording medium is scanned along a direction intersecting the arrangement direction of the recording elements, thereby enabling image recording of the entire surface of the recording medium. The inline method eliminates the need for a transport system such as a carriage for the short scanning nozzles found in reciprocating methods. Furthermore, compared to reciprocating methods, the inline method eliminates the need for complex scanning control involving carriage movement and the recording medium; only the recording medium itself needs to move. Therefore, compared to reciprocating methods, the linear method allows for higher speeds of image recording.

[0126] The application of ink is preferably performed using an inkjet head with a resolution of 300 dpi or higher (more preferably 600 dpi or higher, and even more preferably 800 dpi or higher). Here, dpi is an abbreviation for dots per inch, and 1 inch is 2.54 cm.

[0127] From the viewpoint of obtaining high-definition images, the amount of ink droplets ejected from the nozzle of the inkjet head is preferably 1 pL (picoli) to 10 pL, more preferably 1.5 pL to 6 pL. Furthermore, from the viewpoint of improving image uniformity and the coherence of continuous gray levels, combining different droplet volumes is also effective.

[0128] <Transfer Printing Process> The transfer printing method of the present invention includes a process of transferring an image recorded on a non-permeable substrate onto a fabric.

[0129] As for the types of fibers used in fabrics, examples include synthetic fibers such as nylon, polyester, and acrylonitrile; semi-synthetic fibers such as cellulose acetate and rayon; natural fibers such as cotton, silk, and wool; and mixed fibers composed of two or more types selected from the group consisting of synthetic fibers, semi-synthetic fibers, and natural fibers.

[0130] The preferred fiber type for fabrics is cellulose fiber, and more preferably cotton. Examples of fabric types include woven fabrics, woven textiles, and nonwoven fabrics. Fabrics can also be used for fabric products.

[0131] Examples of textile products include clothing (e.g., T-shirts, sweatshirts, jerseys, trousers, tracksuits, dresses, women's blouses, etc.), bedding, handkerchiefs, etc.

[0132] As a method for transferring an image onto fabric, one example is heating a non-permeable substrate on which the image is recorded and a fabric while the image is in contact with the fabric. The heating temperature is, for example, 100℃~200℃. The heating time is, for example, 20 seconds to 5 minutes.

[0133] Commercially available hot presses can be used in the transfer process. Examples of hot presses include the AF-54TEN type automatic flatbed press (manufactured by Asahi Garment Machinery Co., Ltd.) and the ZEUS PZ-130110D (manufactured by EUROPORT CO.,LTD.).

[0134] In the transfer process, from the viewpoint of improving adhesion, it is preferable to apply a hot melt adhesive to the image-recorded surface of the non-permeable substrate before overlapping the image-recorded non-permeable substrate and the fabric.

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

[0136] The details of the pretreatment solution are as described above. The pretreatment solution can be applied using known application methods such as coating, inkjet recording, and immersion.

[0137] As a coating method, known coating methods include those using bar coaters, die coaters, air knife coaters, blade coaters, bar coaters, knife coaters, extrusion coaters, and reverse roller coaters.

[0138] The details regarding inkjet recording methods are the same as those in the ink application process.

[0139] The non-permeable substrate can be heated before applying the pretreatment solution. The heating temperature can be appropriately set according to the type of non-permeable substrate and the composition of the pretreatment solution, but it is preferable to set the temperature of the non-permeable substrate to 30°C to 70°C, and more preferably to 30°C to 60°C.

[0140] In the pretreatment liquid application process, the pretreatment liquid applied to a non-permeable substrate can be heated and dried. Examples of components used for heating and drying the pretreatment liquid include known heating components such as heaters, known air supply components such as dryers, and components combining these.

[0141] Examples of methods for heating and drying pretreatment liquids include heating the non-permeable substrate from the side opposite to the surface to which the pretreatment liquid is applied using a heater, blowing warm air or hot air onto the surface of the non-permeable substrate to which the pretreatment liquid is applied, heating the non-permeable substrate from the surface to which the pretreatment liquid is applied or from the side opposite to the surface to which the pretreatment liquid is applied using an infrared heater, and combining these methods together.

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

[0143] There is no particular limitation on the heating and drying time, but it is preferably 0.5 seconds to 60 seconds, more preferably 0.5 seconds to 20 seconds, and even more preferably 0.5 seconds to 10 seconds.

[0144] The transfer printing method of the present invention may include a step of applying an external coating liquid to the surface of a non-permeable substrate on which ink has been applied (hereinafter also referred to as the "external coating liquid application step") after the ink application step. Furthermore, the transfer printing and dyeing method of the present invention may include a pretreatment liquid application step, an ink application step, and an external coating liquid application step.

[0145] The details of the topical liquid are as described above. The application of the external coating liquid can be carried out using known application methods such as coating, inkjet recording, and immersion. When the transfer printing and dyeing method of the present invention includes an external coating liquid application step, the step of applying the above-mentioned hot melt adhesive (hereinafter also referred to as the "hot melt adhesive application step") can be omitted. Example

[0146] The present invention will be described in more detail below through embodiments, but the present invention is not limited to the following embodiments as long as it does not depart from its spirit.

[0147] <<Example 1>> [Ink Preparation] <Synthesis of Uncrosslinked Polymer d1> 153.5 parts by weight of tripropylene glycol monomethyl ether (product name "MFTG", manufactured by Nippon Nyukazai Co., LTd.) as a reaction solvent were added to a reaction vessel equipped with a gas inlet pipe, thermometer, condenser and stirrer, and then nitrogen gas was used to replace the gas in the reaction vessel. 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 of the types and mass ratios shown in Table 1 (total 100 parts by mass), and V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) (3.0 parts by mass) as a polymerization initiator was added dropwise over 3 hours to carry out the polymerization reaction. After the dropwise addition was completed, the reaction was further carried out at 85°C for 3 hours to complete the polymerization and obtain a solution containing uncrosslinked polymer d1.

[0148] <Preparation of Uncrosslinked Dispersion of Magenta Pigment> After uniformly dispersing the mixture of the following components, a bead mill (Ashizawa Finetech Ltd., bead diameter: 0.3 mm) is used. The mixture (containing zirconia beads) was dispersed for 3 hours. This yielded an uncrosslinked dispersion of magenta pigment dispersed by the uncrosslinked polymer.

[0149] • Magenta pigment: Pigment red 122…120 parts by weight • 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 sodium hydroxide aqueous solution…125.8 parts by weight Water…230.0 parts by weight

[0150] While stirring the mixture of the following components 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] • Dilute the uncrosslinked dispersion with deionized water to achieve a pigment concentration of 15% by mass…500.0 parts by mass 1 mol / L hydrochloric acid aqueous solution… 19.4 parts by weight ·Pure water…225.2 parts by weight

[0152] <Preparation of Crosslinked Dispersion of Magenta Pigment> The mixture of the following components 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 a crosslinking agent, resulting in a crosslinked dispersion containing a crosslinked polymer p1 and a magenta pigment. • Uncrosslinked dispersion after neutralization with hydrochloric acid… 744.6 parts by weight • Crosslinking agent: “Denacol EX-321” (manufactured by Nagase ChemteX Corporation) (trimethylolpropane polyglycidyl ether)…5.4 parts by weight

[0153] Next, the crosslinked dispersion was centrifuged at 7000G for 20 minutes to remove coarse particles. The centrifuged crosslinked dispersion was then filtered through a 0.5μm LABO-PURE filter manufactured by ROKI Co., Ltd. to remove coarse particles. Furthermore, the filtered crosslinked dispersion was ultrafiltered at a flow rate of 600 mL per minute through an ultrafiltration apparatus (cross-flow ultrafiltration unit (UF), manufactured by Sartorius) equipped with a polyethersulfone (PESU) membrane (micropore size: 0.1 μm). The liquid temperature was adjusted to 25°C, and ultrafiltration was performed 10 times, with each cycle being equal to one volume ratio of the added liquid. Then, ion-exchanged water was added to bring the pigment concentration to 15% by mass, yielding pigment dispersion DM1.

[0154] <Preparation of Magenta Ink> The mixture of the following components was stirred with a magnetic stirrer for 60 minutes and filtered through a LABO-PURE filter (0.5 μm) manufactured by ROKI Co., Ltd. to obtain magenta ink. Pigment dispersion DM1: 33.33% by mass (pigment concentration: 5% by mass) Resin particles: Particles composed of styrene-butadiene copolymer, product name "Rovene 4170", manufactured by Mallard Creek Polymers... 7.5% by weight (based on resin solids). DEGmEE…3% quality PGmME…10% quality Glycerin…10% by mass The total amount of water…magenta ink becomes the balance of 100% by mass.

[0155] <Preparation of Cyan Ink> The magenta pigment was changed to cyan pigment (pigment blue 15:3 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.)) and the pigment concentration was changed to 4% by mass. Otherwise, cyan ink was prepared using the same method as magenta ink.

[0156] <<Examples 2 to 25, Comparative Examples 1 to 5>> The types and contents (mass%) of the components used to synthesize the uncrosslinked polymer were changed to those listed in Table 1. Otherwise, the uncrosslinked polymer was synthesized using the same method as in Example 1. The type of crosslinking agent was changed to that listed in Table 1, and the pigment dispersion was prepared in the same manner as in Example 1. The types and contents (mass%) of the components contained in the ink were changed to those recorded in Table 1. Otherwise, magenta ink and cyan ink were prepared using the same method as in Example 1.

[0157] The detailed information on the components used in the preparation of magenta ink is 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: Isoborneol Methacrylate PDEGA: Phenoxy diethylene 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.), an aqueous crosslinking agent for applying hydrophilic segments to polycarbodiimide resins.

[0160] -Resin particles- •SB: Product name "Rovene 4170", manufactured by Mallard Creek Polymers, consisting of styrene-butadiene copolymer particles. PU1: Product name "SUPERFLEX 460", manufactured by DKS Co. Ltd., composed of polyurethane resin particles. PU2: Product name "SUPERFLEX 860", manufactured by DKS Co. Ltd., consists of particles made of polyurethane resin. PU3: Product name "SUPERFLEX E-4800", manufactured by DKS Co. Ltd., is composed of polyurethane resin particles.

[0161] -Organic solvents- 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 and Magenta Inks> The types and contents (mass%) of the components used to synthesize the uncrosslinked polymer were changed to those listed in Table 4. Otherwise, the uncrosslinked polymer was synthesized using the same method as in Example 1. The type of crosslinking agent was changed to that listed in Table 4, and the pigment dispersion was prepared in the same manner as in Example 1. The types and contents (mass%) of the components contained in the ink were changed to those recorded in Table 4. Otherwise, magenta ink and cyan ink were prepared using the same method as in Example 1.

[0163] <Preparation of Topical Coating> The components listed in Table 4 were stirred with a magnetic stirrer for 60 minutes and then filtered through a LABO-PURE filter (0.5 μm) manufactured by ROKI Co., Ltd. to obtain the external coating solution.

[0164] The details of each component used in the preparation of the external coating solution are as follows.

[0165] -Resin particles- PU1: Product name "SUPERFLEX 460", manufactured by DKS Co. Ltd., composed of polyurethane resin particles. PU4: Product name "SUPERFLEX500M", manufactured by DKS Co. Ltd., is composed of polyurethane resin particles.

[0166] - Organic solvents ·glycerin PG: Propylene Glycol ·PGmME: Propylene Glycol Monomethyl Ether

[0167] -surfactant- Surfynol 465: Manufactured by Nissin Chemical Co., Ltd., an acetylene glycol surfactant. BYK345: Manufactured by BYK Corporation, a silicone-based surfactant. BYK347: Manufactured by BYK Corporation, a silicone-based surfactant.

[0168] -other- • Fabric softener: Product name "SOFTNER Business Use", manufactured by Kao Corporation

[0169] <<Examples 201-204>> <Preparation of Cyan and Magenta Inks> The types and contents (mass%) of the components used to synthesize the uncrosslinked polymer were changed to those listed in Table 5. Otherwise, the uncrosslinked polymer was synthesized using the same method as in Example 1. The type of crosslinking agent was changed to that listed in Table 5, and the pigment dispersion was prepared in the same manner as in Example 1. The types and contents (mass%) of the components contained in the ink were changed to those recorded in Table 5. Otherwise, magenta ink and cyan ink were prepared using the same method as in Example 1.

[0170] <Preparation of Pretreatment Solution> The components listed in Table 5 were stirred for 60 minutes using a magnetic stirrer and then filtered using a LABO-PURE filter (0.5 μm) manufactured by ROKI Co., Ltd. to obtain the pretreated solution.

[0171] The details of each component used in the preparation of the pretreatment solution are as follows.

[0172] -Flocculant- Calcium nitrate • Cationic polymer: Product name "Catiomaster PD-7", manufactured by Yokkaichi Chemical Company Limited ·Malondiic acid

[0173] -Resin particles- PU4: Product name "SUPERFLEX500M", manufactured by DKS Co. Ltd., is composed of polyurethane resin particles.

[0174] - Organic solvents PG: Propylene Glycol ·PGmME: Propylene Glycol Monomethyl Ether

[0175] -surfactant- Surfynol 465: Manufactured by Nissin Chemical Co., Ltd., an acetylene glycol surfactant. • EMULGEN 103: Manufactured by Kao Corporation, polyoxyethylene lauryl ether BYK345: Manufactured by BYK Corporation, a silicone-based surfactant. • BYK347: Manufactured by BYK Corporation, a silicone-based surfactant.

[0176] <<Examples 301 to 305>> <Preparation of Cyan and Magenta Inks> The types and contents (mass%) of the components used to synthesize the uncrosslinked polymer were changed to those listed in Table 6. Otherwise, the uncrosslinked polymer was synthesized using the same method as in Example 1. The type of crosslinking agent was changed to that listed in Table 6, and the pigment dispersion was prepared in the same manner as in Example 1. The types and contents (mass%) of the components contained in the ink were changed to those recorded in Table 6. Otherwise, magenta ink and cyan ink were prepared using the same method as in Example 1.

[0177] <Preparation of Pretreatment Solution> The components listed in Table 6 were stirred with a magnetic stirrer for 60 minutes and then filtered through a LABO-PURE filter (0.5 μm) manufactured by ROKI Co., Ltd. to obtain the pretreated solution.

[0178] <Preparation of Topical Coating> The components listed in Table 6 were stirred for 60 minutes using a magnetic stirrer and then filtered using a LABO-PURE filter (0.5 μm) manufactured by ROKI Co., Ltd. to obtain the external coating solution.

[0179] [Transfer Printing and Dyeing] <Preparation of Image Recording Device> Prepared Figure 1 The image recording device shown. Inkjet application was used as the pretreatment liquid application device P1. The drying method in the pretreatment liquid drying zone DP1 is set to warm air drying. The first inkjet head IJ1 is equipped with an inkjet head for ejecting cyan ink, and the second inkjet head IJ2 is equipped with an inkjet head for ejecting magenta ink. This allows it to pass directly through the first drying zone D1. The drying method in the second drying zone D2 is set to warm air drying. An air-cooling zone and a hot-melt adhesive application process or an external coating liquid application process (not shown) are provided between the second drying zone D2 and the winding device R2. Both the first inkjet head IJ1 and the second inkjet head IJ2 use 1200dpi (dots per inch, 1 inch is 2.54cm) / 20-inch wide piezoelectric printheads (2048 nozzles in total). The driving frequency of both the first inkjet head IJ1 and the second inkjet head IJ2 is set to 30kHz.

[0180] In Examples 1 through 25, no pretreatment solution was applied; instead, cyan ink and magenta ink were applied sequentially using an inkjet printing method, resulting in an application rate of 6.7 g / m² per unit area. 2 And the hot melt adhesive application process was implemented.

[0181] In Examples 101 to 106, no pretreatment solution was applied; instead, cyan ink and magenta ink were applied sequentially using an inkjet printing method, resulting in an application rate of 6.7 g / m² per unit area. 2 Furthermore, instead of applying a hot-melt adhesive, the coating liquid is applied using an inkjet printing method, resulting in an application rate of 6.7 g / m² per unit area. 2 .

[0182] In Examples 201 to 204, the pretreatment solution was applied using an inkjet recording method, such that the application amount per unit area was 3.0 g / m². 2 Subsequently, cyan ink and magenta ink were applied sequentially using inkjet printing to achieve an application rate of 6.7 g / m² per unit area. 2 And the hot melt adhesive application process was implemented.

[0183] In Examples 301 to 305, the pretreatment solution was applied using an inkjet printing method, such that the amount applied per unit area was 3.0 g / m². 2 Subsequently, cyan ink and magenta ink were applied sequentially using inkjet printing to achieve an application rate of 6.7 g / m² per unit area. 2 Furthermore, instead of applying a hot-melt adhesive, the coating liquid is applied using an inkjet printing method, resulting in an application rate of 6.7 g / m² per unit area. 2 .

[0184] <Image Recording> The image was recorded using the image recording device described above. The image recording device is equipped with pretreatment liquid, cyan ink, and magenta ink. As a non-permeable substrate, a DTF membrane (product name "DTF-H60", manufactured by Cellcam (600mm×100m)) was used. First, the non-permeable substrate is unwound by the unwinding device R1 and conveyed under tension. In Examples 201-204 and Examples 301-305, a pretreatment liquid is applied to the conveyed non-permeable substrate by the pretreatment liquid application device P1. Furthermore, as a non-permeable substrate, it can also be used with OPP membranes (product name "PYLEN FILM-OT", manufactured by TOYOBOCO., LTD., with a thickness of 25μm).

[0185] Next, the pretreatment solution is dried in the pretreatment solution drying zone DP1. The drying conditions for the pretreatment solution are set to be dried for 3 seconds in warm air at 40°C.

[0186] In Examples 1-25 and Examples 101-106, cyan ink is applied to a non-permeable substrate by the first inkjet head IJ1 and allowed to pass directly through the first drying zone D1. In Examples 201-204 and Examples 301-305, cyan ink is applied to the area of ​​the non-permeable substrate to which the pretreatment liquid is applied through the first inkjet head IJ1, and then passes directly through the first drying zone D1.

[0187] Magenta ink was applied to the area on the non-permeable substrate where cyan ink had been applied, using the second inkjet head IJ2.

[0188] Dry the magenta ink in the second drying zone D2.

[0189] An image record is obtained by recording a multicolor image, which is an image derived from cyan ink, overlaid on an image derived from cyan ink, on a non-permeable substrate.

[0190] The obtained image recordings were air-cooled. In Examples 101-106 and Examples 301-305, an external coating liquid was applied to the image of the image recorder and dried, and the image recorder was wound up using a winding device R2.

[0191] In Examples 1-25 and Examples 201-204, a hot melt adhesive (product name "O-Powder", manufactured by CELLCAM INC.) was applied to the image of the image recorder and then heated to melt (bake). The application of the hot melt adhesive, the melting (baking), and the winding of the image recorder were performed using a commercially available DTF powder shaker, the SELSHAKE-mini (manufactured by CELLCAM INC.). The image recording was then unfolded and cut. The cut image recording was overlapped with the fabric and pressed together at 160°C for 2 minutes using a hot press to peel off the non-permeable substrate, thus obtaining the printed material. Additionally, a benchtop automatic flatbed press, model AF-54TEN (manufactured by Asahi Garment Machinery Co., Ltd.), was used for the transfer printing.

[0192] [evaluate] The ejectibility was evaluated using cyan ink. The obtained printed and dyed materials were used to evaluate the washing fastness under warm water conditions, the bleeding of secondary colors, and the image peeling caused by washing and drying.

[0193] <Ejaculatory> The ejectibility of cyan ink was evaluated using ink that had been heated at 80°C for one day after it was freshly prepared. One image record obtained through visual observation was used to identify the number of streaks and ejection delay along the transport direction of the non-permeable substrate in the monochrome image (solid background image). Ejection delay was determined based on whether the ejection time of the initial ink droplet ejected from the inkjet head was delayed relative to a specified time. The evaluation criteria are as follows. AA: There are more than 0 stripes and less than 2 stripes, and no ejection delay was observed. A: There are more than 2 stripes but less than 10 stripes, and no ejection delay was observed. B: There are more than 10 but less than 20 stripes, and no ejection delay was observed. C: There are more than 0 stripes and less than 20 stripes, and an ejection delay is observed. D: There are more than 20 stripes, and a delay in ejection is observed.

[0194] <Wash fastness under warm water conditions> In the evaluation of wash fastness under warm water conditions (in the table, “Warm Water Wash Fastness”), solid images are recorded using cyan ink and magenta ink. The dyed fabric was automatically added to a front-loading washing machine (product name "FLK842-W", manufactured by IRIS OYAMA Co., Ltd.) with 380g of Attack ZERO front-loading detergent (manufactured by Kao Corporation) and washed once in warm water at 40°C. Each sheet of fabric was placed in a washing net for washing. After washing, the wrinkles were smoothed out and the fabric was laid flat to air dry. The evaluation criteria are as follows: Colorimetric measurements of the dyed fabric were performed using a fluorescence spectrophotometer (product name "FD-7", manufactured by Konica Minolta, Inc.) before and after warm water washing. The colorimetric result before washing was set as L. a b The colorimetric result after washing with warm water is set as L. a b . ΔE is calculated by the following formula. A: The difference in ΔE between the printed and dyed materials before and after washing with warm water is less than 4. B: The difference in ΔE between the printed and dyed materials before and after washing with warm water exceeds 4 but is less than 8. C: The difference in ΔE between the printed and dyed materials before and after washing with warm water exceeds 8 but is less than 12. D: The difference in ΔE between the printed and dyed materials before and after washing with warm water exceeds 12.

[0195] <Secondary color bleeding> In the evaluation of secondary color bleeding (referred to as "secondary color bleeding" in the table), cyan ink was used to record the text image, and magenta ink was used to record the solid background image. The text images were set to 16pt in size, using the MSP Gothic format for "A, B, C". The text images on the printed fabric were visually observed. First, determine whether there is blurring of text or images when magenta ink is sprayed after cyan ink has been sprayed without drying. In the case of blurred text images, determine whether there is blurring of text images by spraying cyan ink, drying at 80°C for 2 seconds, and then spraying magenta ink. In the case of blurred text images, determine whether there is blurring of text images by spraying cyan ink, drying at 80°C for 4 seconds, and then spraying magenta ink. In the case of blurred text images, determine whether there is blurring of text images by spraying cyan ink, drying at 80°C for 8 seconds, and then spraying magenta ink. The experiment ends at the point in time if there is no blurring of text or images. The evaluation criteria are as follows. AA: Even if the cyan ink is not dried after being sprayed, there will be no blurring of the text or image. A: After the cyan ink is sprayed out and dried for 2 seconds, there is no blurring of the text or image. B: After the cyan ink is sprayed and dried for 4 seconds, there is no blurring of the text or image. C: After the cyan ink is sprayed and dried for 8 seconds, there is no blurring of the text or image. D: The text image is blurred after the cyan ink is sprayed and dried for 8 seconds.

[0196] <Image peeling caused by washing and drying> In the evaluation of image peeling caused by washing and drying (“Drying Image Peeling” in the table), solid images were recorded using cyan ink and magenta ink. The Attack ZERO front-loading washing machine (380g, manufactured by Kao Corporation) was automatically filled into a drum-type washing machine (product name "FLK842-W", manufactured by IRIS OH YAMA CO.,LTD.), and the printed fabric was washed twice on a 40°C warm water setting. The fabric was then washed one sheet at a time in the washing net. After washing, the fabric was tumble-dried on an automatic drying machine. After drying, any image peeling was visually inspected. The experiment was terminated without confirming image stripping. If image peeling is confirmed, the printed material is washed once in warm water at 40°C. Otherwise, the same operation as described above is performed to confirm whether image peeling has occurred. The evaluation criteria are as follows. A: After two cycles of warm water washing and tumble drying, no image peeling was detected. B: No image peeling was detected after one cycle of warm water washing and tumble drying. C: After one cycle of warm water washing and tumble drying, image peeling with a width of less than 1mm was confirmed. D: In the printed material after one cycle of warm water washing and drum drying, image peeling with a width greater than 1 mm was confirmed.

[0197] The evaluation results are shown in Tables 1 through 6. Tables 1 to 6 list the types and contents (mass %) of polymeric monomers used in the synthesis of the crosslinked polymers contained in the inks. The proportion of hydrophobic monomers (mass %) refers to the proportion of hydrophobic monomers in the polymeric monomers used in the synthesis of the crosslinked polymers. T D It refers to the glass transition temperature of cross-linked polymers. T L It refers to the glass transition temperature of resin particles. Furthermore, the type and number of functional groups of the crosslinking agent used in the synthesis of the crosslinked polymer are recorded. In Comparative Examples 1 to 3 and Comparative Example 5, since no crosslinking agent was used, it was recorded as "-" in the crosslinking agent column.

[0198] [Table 1]

[0199] [Table 2]

[0200] [Table 3]

[0201] [Table 4]

[0202] [Table 5]

[0203] [Table 6]

[0204] As shown in Tables 1 to 3, in Examples 1 to 25, it can be seen that because it contains water, pigment, cross-linked polymer and resin particles, with the resin particle content being 5% by mass or more, it has excellent sprayability. Moreover, in the printed and dyed materials, it has excellent wash fastness under warm water conditions, and image peeling caused by washing and drying is suppressed. On the other hand, in Comparative Example 1, since it did not contain cross-linked polymers and the content of resin particles was less than 5% by mass, all evaluation results were D. In Comparative Example 2, since it does not contain cross-linked polymers, it exhibits poor sprayability and wash fastness under warm water conditions, and image peeling due to drying was observed. In Comparative Example 3, since it did not contain cross-linked polymers, it had poor ejectibility, and image peeling due to drying was observed. In Comparative Example 4, it can be seen that the content of resin particles is less than 5% by mass, and the wash fastness under warm water conditions is poor. In Comparative Example 5, since it did not contain cross-linked polymers, the ejection performance was slightly worse, and image peeling due to drying was observed.

[0205] In Example 25, it is known that the product also contains an organic solvent with an SP value of 26 or less, and the content of the organic solvent with an SP value of 26 or less is 3% by mass or more. Compared with Example 24, the bleeding of the secondary color is suppressed.

[0206] In Examples 2 and 3, it is evident that the crosslinked polymer is crosslinked by an epoxy compound, and compared to Example 4, image peeling caused by drying is suppressed.

[0207] In Example 11, the glass transition temperature T of the crosslinked polymer is known. D At temperatures above 50°C, the washing fastness under warm water conditions is excellent compared to Example 12, and image peeling caused by drying is suppressed.

[0208] In Example 13, the glass transition temperature T of the resin particles is known. L At temperatures below 30°C, the washing fastness under warm water conditions is excellent compared to Example 17, and image peeling caused by drying is suppressed.

[0209] In Example 12, it can be seen that "T" D -T L "At temperatures above 50°C, the washing fastness with warm water is excellent compared to Example 17." In Example 13, it can be seen that "T" D -T L "The temperature is below 160°C. Compared with Example 18, it has excellent sprayability, excellent wash fastness under warm water conditions, and image peeling caused by drying is suppressed."

[0210] Furthermore, as shown in Table 5, it can be seen that the use of pretreatment solution can significantly suppress the bleeding of secondary color. Furthermore, it is known that when using an external coating liquid, transfer printing and dyeing can be carried out without the application of a hot melt adhesive.

[0211] Furthermore, it is known that in Example 1, even when a commercially available crosslinking dispersion (product name "APD1000Magenta", manufactured by Fujifilm Imaging Colorants) was used instead of pigment dispersion DM1, the same evaluation results were obtained. Furthermore, it is known that in Example 301, even when using an anilox roller to make the application amount per unit area 6.7 g / m², 2 The same evaluation results can be obtained when the topical liquid is applied in the same manner.

[0212] Furthermore, the entire disclosure of Japanese Patent Application No. 2024-048727, filed on March 25, 2024, is incorporated herein by reference. Moreover, all documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as those specifically and separately described and incorporated herein by reference.

Claims

1. A transfer printing ink, comprising water, pigment, a cross-linked polymer, and resin particles. The content of the resin particles is 5% or more by mass relative to the total amount of ink used for transfer printing and dyeing.

2. The transfer printing ink according to claim 1, wherein, It also contains organic solvents with an SP value of less than 26. The content of organic solvents with an SP value of 26 or less is 3% by mass or more relative to the total amount of ink used for transfer printing and dyeing.

3. The transfer printing ink according to claim 1, wherein, The polymer with a cross-linked structure is cross-linked by an epoxy compound.

4. The transfer printing ink according to claim 1, wherein, The glass transition temperature T of the polymer with the cross-linked structure D Temperatures above 50°C.

5. The transfer printing ink according to claim 1, wherein, The glass transition temperature T of the resin particles L The temperature is below 30℃.

6. The transfer printing ink according to claim 1, wherein, The glass transition temperature T of the polymer with the cross-linked structure D and the glass transition temperature T of the resin particles L It satisfies the following equation (1). 50℃≤T D -T L ≤160℃ (1)。 7. The transfer printing ink according to claim 2, wherein, The organic solvent with 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 with a cross-linked structure is a cross-linked polymer, wherein the content of structural units derived from polymeric monomers having at least one hydrophobic group selected from the group consisting of alkyl and aromatic hydrocarbon groups with more than 10 carbon atoms is 50% by mass or more.

9. A transfer printing ink set, comprising: A transfer printing ink contains water, pigments, a cross-linked polymer, 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; and External coating liquid containing resin particles.

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

11. The ink set for transfer printing and dyeing according to claim 9, wherein, The external coating 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 The pretreatment solution contains a coagulant.

13. A transfer printing ink set, comprising: Transfer printing ink as described in any one of claims 1 to 8; The external coating solution for transfer printing and dyeing contains resin particles; and The pretreatment solution contains a coagulant.

14. A transfer printing method, comprising the following steps: To record an image by applying the transfer printing ink according to any one of claims 1 to 8 onto a non-permeable substrate; and The image recorded on the non-permeable substrate is transferred onto the fabric.

Images