Resin particle composition for DTF printing and method for producing resin particle composition for DTF printing

Abstract

This resin particle composition for DTF printing contains thermoplastic polyurethane resin particles (A), a plasticizer (B), and fine particles (C) different from the thermoplastic polyurethane resin particles (A). The plasticizer (B) content is 5-60 wt% based on the weight of the thermoplastic polyurethane resin particles (A), and the fine particle (C) content is 0.1-10 wt% based on the weight of the thermoplastic polyurethane resin particles (A).

Description

Resin particle composition for DTF printing and method for producing resin particle composition for DTF printing

[0001] The present invention relates to a resin particle composition for DTF printing and a method for producing a resin particle composition for DTF printing.

[0002] Conventionally, known methods for printing images on textile products include screen printing and DTG (Data To Garment) printing, which involves directly inkjet printing on textile products. In addition to these methods, DTF (Direct To Film) printing has been attracting attention in recent years. In DTF printing, rather than directly printing an image on a textile product, an image is printed on a film using an inkjet or the like, and thermoplastic resin particles are placed on the printed image and then thermally compressed onto the textile product to transfer the image to the textile product. In DTF printing, the properties of the thermoplastic resin particles have a significant impact on the operability of the print and the accuracy and fastness of the printed image. For this reason, research and development is underway to find thermoplastic resin particles suitable for DTF printing.

[0003] For example, Patent Document 1 describes a white urethane powder containing titanium oxide powder that can print color images with excellent sharpness and washability in DTF printing. However, the white urethane powder described in Patent Document 1 has problems such as poor powder flow and poor operability, and the powder is not evenly distributed on the ink, making it difficult to obtain a uniform printed surface.

[0004] Japanese Patent Application Laid-Open No. 2023-145316

[0005] An object of the present invention is to provide a resin particle composition for DTF printing that is applicable to water-based inks (high hydrophobicity) and produces printed images with high durability (high fastness).

[0006] As a result of intensive research aimed at solving these problems, the present invention has been arrived at. Specifically, the present invention relates to a resin particle composition for DTF printing containing thermoplastic polyurethane resin particles (A), a plasticizer (B), and fine particles (C) different from the thermoplastic polyurethane resin particles (A), wherein the content of the plasticizer (B) is 5 to 60 wt % based on the weight of the thermoplastic polyurethane resin particles (A), and the content of the fine particles (C) is 0.1 to 10 wt % based on the weight of the thermoplastic polyurethane resin particles (A), and a method for producing a resin particle composition for DTF printing containing thermoplastic polyurethane resin particles (A), a plasticizer (B), and fine particles (C) different from the thermoplastic polyurethane resin particles (A), wherein the thermoplastic polyurethane resin particles (A) contain a plasticizer (B) and a fine particle (C) different from the thermoplastic polyurethane resin particles (A), the thermoplastic polyurethane resin particles (A) are made of a thermoplastic polyurethane resin obtained by reacting an isocyanate group-terminated urethane prepolymer (a1) with an amine (a2), the content of the plasticizer (B) is 5 to 60 wt % based on the weight of the thermoplastic polyurethane resin particles (A), and the content of the fine particles (C) is 0.1 to 10 wt % based on the weight of the thermoplastic polyurethane resin particles (A), and the method for producing a resin particle composition for DTF printing includes a step of mixing and stirring a mixture (M) containing the amine (a2), an organic solvent (K) having a relative dielectric constant of 5 to 25, and water with the isocyanate group-terminated urethane prepolymer (a1) to obtain the thermoplastic polyurethane resin particles (A).

[0007] According to the present invention, it is possible to provide a resin particle composition for DTF printing that is applicable to water-based inks (high hydrophobicity) and produces printed images with high durability (high fastness).

[0008] The present invention is directed to a resin particle composition for DTF printing, which comprises thermoplastic polyurethane resin particles (A), a plasticizer (B), and fine particles (C) different from the thermoplastic polyurethane resin particles (A).

[0009] <Thermoplastic polyurethane resin particles (A)> The thermoplastic polyurethane resin particles (A) of the present invention preferably have a volume average particle diameter of 100 to 300 μm. If the volume average particle diameter of the thermoplastic polyurethane resin particles (A) is less than 100 μm, the texture during DTF printing may deteriorate, while if it exceeds 300 μm, the transfer melting properties during DTF printing may deteriorate. From the viewpoint of achieving both a good texture and a good transfer melting properties, the volume average particle diameter of the thermoplastic polyurethane resin particles (A) is preferably 165 to 230 μm, and more preferably 195 to 225 μm.

[0010] The volume average particle diameter of the thermoplastic polyurethane resin particles (A) can be measured using a laser diffraction particle size distribution analyzer [e.g., "MicrotracMT3000II" manufactured by Nikkiso Co., Ltd.]. 20 g of the thermoplastic polyurethane resin particles (A) and 100 g of a 2% by weight aqueous solution of the dispersant "Sunspearl PS-800" (manufactured by Sanyo Chemical Industries, Ltd.) are mixed and stirred for 1 minute or more to form a measurement sample, and the measurement conditions can be as follows. The obtained MV (Mean Volume Diameter) is taken as the volume average particle diameter of the thermoplastic polyurethane resin particles (A). <Measurement Conditions> Set Zero Time: 30 seconds Measurement Time: 30 seconds Number of Measurements: 2 Particle Transmittance: Transmitted Particle Refractive Index: 1.59 Particle Shape: Aspherical Solvent: Water Solvent Refractive Index: 1.333

[0011] The thermoplastic polyurethane resin particles (A) are preferably made of a thermoplastic polyurethane resin obtained by reacting an aliphatic diisocyanate (a1-1), a monool (a1-2), a diol (a1-3) having a number average molecular weight of 500 to 10,000, and an amine (a2).

[0012] Examples of the aliphatic diisocyanate (a1-1) include (i) aliphatic diisocyanates having 4 to 20 carbon atoms [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc.], and (ii) alicyclic diisocyanates having 6 to 18 carbon atoms [isophorone diisocyanate (IPD (I), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene, etc.; (iii) aralkyl diisocyanates having 10 to 18 carbon atoms [m- or p-xylylene diisocyanate (XDI), α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI), etc.]; (iv) modified products of these diisocyanates (diisocyanate modified products having a carbodiimide group, a uretdione group, a uretoimine group, a urea group, etc.), and mixtures of two or more of these. Among these, preferred are aliphatic diisocyanates having 4 to 20 carbon atoms and alicyclic diisocyanates having 6 to 18 carbon atoms, and particularly preferred are HDI, IPDI, and hydrogenated MDI. As the aliphatic diisocyanate (a1-1), HDI (hexamethylene diisocyanate) is more preferred.

[0013] Examples of the monool (a1-2) include aliphatic monools having 1 to 8 carbon atoms [straight-chain monools (e.g., methanol, ethanol, propanol, butanol, pentanol, hexanol, and octanol), branched monools (e.g., isopropyl alcohol, neopentyl alcohol, 3-methylpentanol, and 2-ethylhexanol)], monools having 6 to 10 carbon atoms and a cyclic group [e.g., alicyclic group-containing monools (e.g., cyclohexanol) and aromatic ring-containing monools (e.g., benzyl alcohol)], polymeric monools (e.g., polyester monools, polyether monools, and polyetherester monools), and mixtures of two or more of these. Among these, aliphatic monools or aromatic ring-containing monools having 1 to 8 carbon atoms are preferred. Benzyl alcohol is preferred as the monool (a1-2).

[0014] Examples of the diol (a1-3) include polyester diols, polyether diols, polyether ester diols, polycarbonate diols, polyether carbonate diols, and mixtures of two or more of these.

[0015] Examples of polyester diols include (i) those obtained by condensation polymerization of a low-molecular-weight diol with a dicarboxylic acid or an ester-forming derivative thereof [such as an acid anhydride, a lower alkyl (having 1 to 4 carbon atoms) ester, and an acid halide] or a dialkyl carbonate (with an alkyl group having 1 to 4 carbon atoms); (ii) those obtained by ring-opening polymerization of a lactone monomer using a low-molecular-weight diol as an initiator; (iii) those obtained by reacting a dicarboxylic acid anhydride and an alkylene oxide (hereinafter abbreviated as AO) using a low-molecular-weight diol as an initiator; and mixtures of two or more of these.

[0016] Specific examples of the low-molecular-weight diol in (i), (ii) and (iii) include aliphatic diols having 2 to 8 carbon atoms [linear diols (ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc.), branched diols (propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,2-, 1,3- or 2,3-butanediol, etc.)], diols having a cyclic group [diols having 6 to 15 carbon atoms Examples of suitable diols include alicyclic group-containing diols (such as 1,4-bis(hydroxymethyl)cyclohexane and hydrogenated bisphenol A), aromatic ring-containing diols having 8 to 20 carbon atoms (such as m- or p-xylylene glycol and bis(2-hydroxyethyl)terephthalate), AO adducts thereof (molecular weight less than 500), monocyclic dihydric phenols (such as catechol and hydroquinone), AO adducts (molecular weight less than 500) of bisphenols (such as bisphenol A, bisphenol S and bisphenol F) or polynuclear phenols (such as dihydroxynaphthalene), and mixtures of two or more of these. Among these, preferred are aliphatic diols having 2 to 8 carbon atoms and alicyclic group-containing diols having 6 to 15 carbon atoms.

[0017] Examples of the AO include AOs having 2 to 4 carbon atoms [ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3-, 1,4- or 2,3-butylene oxide], styrene oxide, α-olefin oxides having 5 to 10 or more carbon atoms, epichlorohydrin, and combinations of two or more of these (block or random addition).

[0018] Specific examples of the (i) dicarboxylic acid or ester-forming derivative thereof include aliphatic dicarboxylic acids having 4 to 16 carbon atoms [succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.], aromatic dicarboxylic acids having 8 to 12 carbon atoms [terephthalic acid, isophthalic acid, orthophthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc.], ester-forming derivatives thereof [acid anhydrides (phthalic anhydride, maleic anhydride, etc.), lower alkyl esters (dimethyl esters, diethyl esters, etc.), acid halides (acid chlorides, etc.)], and mixtures of two or more thereof.

[0019] The lactone monomer (ii) includes lactones having 4 to 12 carbon atoms (for example, γ-butyrolactone, γ-valerolactone, and ε-caprolactone) and mixtures of two or more of these.

[0020] Examples of the polyether diol include AO adducts of the above-mentioned low molecular weight diols. Preferred examples of the polyether diol include polyoxytetramethylene glycol, AO adducts of monocyclic dihydric phenols, AO adducts of bisphenols, and AO adducts of polynuclear phenols, and more preferred examples are EO adducts of bisphenols.

[0021] Examples of polyetherester diols include those obtained by using the polyether diols described above in place of the low-molecular-weight diols used as raw materials in the polyester diols described above, such as those obtained by condensation polymerization of one or more of the polyether diols described above with one or more of the dicarboxylic acids or ester-forming derivatives thereof exemplified as raw materials for the polyester diols described above.

[0022] The polycarbonate diol is not particularly limited, but examples thereof include those obtained by reacting the low molecular weight diol with a carbonate compound such as alkylene carbonate, dialkyl carbonate, diaryl carbonate, and the like.

[0023] The polyether carbonate diol is not particularly limited, but examples thereof include those obtained by reacting the above-mentioned polyether diol with a carbonate compound such as alkylene carbonate, dialkyl carbonate, diaryl carbonate, and the like.

[0024] The number average molecular weight of the diol (a1-3) is 500 to 10,000. If the number average molecular weight of the diol (a1-3) is less than 500, the meltability of the resin particle composition for DTF printing may deteriorate, while if it exceeds 10,000, the durability of the printed surface obtained from the resin particle composition for DTF printing may decrease, and the texture of the molded article may deteriorate. From the viewpoint of achieving a balance between the meltability of the resin particle composition for DTF printing, the durability of the printed surface, and the texture of the molded article, the number average molecular weight of the diol (a1-3) is preferably 800 to 5,000, more preferably 800 to 4,000, and even more preferably 900 to 3,000.

[0025] The number average molecular weight of the diol (a1-3) is measured by gel permeation chromatography using a Waters Alliance 2695 measuring instrument manufactured by Waters Corporation, tetrahydrofuran (hereinafter abbreviated as THF) as a solvent, and polystyrene as a molecular weight standard substance.

[0026] Preferred combinations of components constituting the thermoplastic polyurethane resin particles (A) are as follows: a combination of an aliphatic diisocyanate having 4 to 20 carbon atoms as the aliphatic diisocyanate (a1-1), an aromatic ring-containing monool as the monool (a1-2), a polyester diol as the diol (a1-3) having a number average molecular weight of 500 to 10,000, and an aliphatic diamine having 2 to 12 carbon atoms as the amine (a2); and a combination of hexamethylene diisocyanate having 4 to 20 carbon atoms as the aliphatic diisocyanate (a1-1), benzyl alcohol as the monool (a1-2), polyethylene isophthalate and / or polybutylene adipate as the diol (a1-3) having a number average molecular weight of 500 to 10,000, and hexamethylene diamine as the amine (a2).

[0027] The thermoplastic polyurethane resin particles (A) of the present invention can be obtained by reacting an aliphatic diisocyanate (a1-1), a monool (a1-2), a diol (a1-3) having a number average molecular weight of 500 to 10,000, and an amine (a2) by a known method. Among these, it is preferable to obtain the thermoplastic polyurethane resin particles (A) by reacting an isocyanate-terminated urethane prepolymer (a1) obtained by reacting the aliphatic diisocyanate (a1-1), the monool (a1-2), and the diol (a1-3) with the amine (a2). The reaction temperature for producing the isocyanate-terminated urethane prepolymer (a1) may be the same as the temperature conventionally used for urethanization, i.e., 20 to 100°C when a solvent is used, and 20 to 220°C, preferably 80 to 200°C, when no solvent is used.

[0028] When producing the isocyanate group-terminated urethane prepolymer (a1), an isocyanate group-terminated prepolymer can be obtained by using an aliphatic diisocyanate (a1-1) in such a way that the molar amount of isocyanate groups is in excess relative to the total molar amount of terminal hydroxyl groups of the monool (a1-2) and the diol (a1-3).

[0029] In the reaction for producing the isocyanate group-terminated urethane prepolymer (a1), a catalyst conventionally used in polyurethanes can be used to promote the reaction, if necessary. Examples of such catalysts include amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.) and tin catalysts (trimethyltin laurate, dibutyltin dilaurate, dibutyltin maleate, etc.).

[0030] Furthermore, when producing the isocyanate group-terminated urethane prepolymer (a1), a diol having 4 to 6 carbon atoms may be added as a chain extender. Examples of the diol having 4 to 6 carbon atoms include 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.

[0031] Examples of the amine (a2) to be reacted with the isocyanate group-terminated urethane prepolymer (a1) include alicyclic diamines and aliphatic amines. Among the amines (a2), examples of the alicyclic diamines include alicyclic diamines having 6 to 18 carbon atoms (4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, diaminocyclohexane, isophoronediamine, etc.). Examples of the aliphatic diamines include aliphatic diamines having 2 to 12 carbon atoms (ethylenediamine, propylenediamine, hexamethylenediamine, etc.) and aromatic aliphatic diamines having 8 to 15 carbon atoms (xylylenediamine, α,α,α',α'-tetramethylxylylenediamine, etc.). These may be used alone or in combination of two or more. Of these, preferred are isophoronediamine and hexamethylenediamine.

[0032] The thermoplastic polyurethane resin particles (A) can be produced by mixing and stirring an amine (a2), a mixture (M) containing water and an organic solvent (K) having a relative dielectric constant of 5 to 25, and an isocyanate group-terminated urethane prepolymer (a1). In this process, primary particle formation and coalescence of the primary particles can be carried out in parallel in the aqueous medium.

[0033] Specifically, the following steps (I) and (II) are carried out. Step (I): A mixture (M) is prepared, which is a mixture of an amine (a2), an organic solvent (K) having a relative dielectric constant of 5 to 25, and water. Step (II): The mixture (M) and an isocyanate group-terminated urethane prepolymer (a1) are mixed and stirred to obtain thermoplastic polyurethane resin particles (A).

[0034] The organic solvent (K) is an organic solvent having a relative dielectric constant of 5 to 25. The relative dielectric constant is preferably 6 to 24, and more preferably 7 to 23. The relative dielectric constant ε can be expressed by the following equation, assuming that when a sample substance is filled between the electrodes of a parallel-plate capacitor having a capacitance of C0 in a vacuum, the capacitance becomes C: ε = C / C0. The relative dielectric constants of the main organic solvents preferably used in the present invention are as follows: acetone has a relative dielectric constant of 21.5, MEK (methyl ethyl ketone) has a relative dielectric constant of 15.5, THF (tetrahydrofuran) has a relative dielectric constant of 8.2, and methyl acetate has a relative dielectric constant of 6.7.

[0035] If the dielectric constant of the organic solvent (K) is less than 5, the organic solvent (K) and the surfactant described below are difficult to mix, so that granulation due to particle coalescence does not occur, and particles with an uneven surface cannot be obtained.If the dielectric constant exceeds 25, the dielectric constant of the mixture (M) becomes too high, so that granulation due to particle coalescence does not occur, and particles with an uneven surface cannot be obtained.

[0036] Examples of the organic solvent (K) include ketones, alcohols, ethers, esters, and combinations of two or more of these. Preferred is at least one selected from the group consisting of ketones having 3 to 9 carbon atoms, ethers having 4 to 8 carbon atoms, and esters having 3 to 6 carbon atoms.

[0037] Examples of ketones having 3 to 9 carbon atoms include acetone, MEK, MIBK, diethyl ketone, etc. Examples of ethers having 4 to 8 carbon atoms include THF, etc. Examples of esters having 3 to 6 carbon atoms include methyl acetate, ethyl acetate, etc. Among these, acetone, MEK, THF, and methyl acetate are preferred.

[0038] The mixture (M) may further contain a dispersion stabilizer. Examples of dispersion stabilizers include water-soluble polymers (methyl cellulose, polyvinyl alcohol, polyethylene glycol, polyacrylates, polyvinylpyrrolidone, sodium salts of copolymers of diisobutylene and maleic acid, etc.), inorganic powders (calcium carbonate powder, calcium phosphate powder, hydroxyapatite powder, silica powder, etc.), and surfactants (sodium dodecylbenzenesulfonate, sodium laurate, polycarboxylic acid-type anionic surfactants, etc.). The amount of dispersion stabilizer used is preferably 10% by weight or less, more preferably 0.001 to 8% by weight, and even more preferably 0.01 to 5% by weight, based on the weight of water. Within this range, the physical properties of the resin are not affected.

[0039] From the viewpoint of easily obtaining thermoplastic polyurethane resin particles (A) with any particle diameter and any particle size distribution, it is preferable that the mixture (M) contains a dispersion stabilizer.

[0040] The content of the organic solvent (K) is preferably 5 to 30 wt%, more preferably 7 to 27 wt%, and even more preferably 10 to 25 wt%, based on the total weight of the mixture (M) and the isocyanate group-terminated urethane prepolymer (a1). When the content of the organic solvent (K) is 5 wt% or more based on the total weight of the mixture (M) and the isocyanate group-terminated urethane prepolymer (a1), granulation due to particle coalescence occurs, making it easier to obtain particles with an uneven surface. Furthermore, when the content of the organic solvent (K) is 30 wt% or less, granulation due to particle coalescence can be controlled, making it easier to obtain particles with a desired volume average particle size.

[0041] The amount of amine (a2) in mixture (M) is preferably 0.50 to 1.50 equivalents, more preferably 0.70 to 1.20 equivalents, even more preferably 0.70 to 1.00 equivalents, and particularly preferably 0.70 to 0.90 equivalents, relative to 1 equivalent of isocyanate groups in isocyanate-group-terminated urethane prepolymer (a1). Within this range, thermoplastic polyurethane resin particles (A) that combine transfer meltability and texture are easily obtained.

[0042] The temperature during preparation of the mixture (M) in step (I) is preferably 10 to 40°C, the peripheral speed is preferably 0.05 to 5.0 m / s, and the mixing time is preferably 1 to 5 minutes. The mixture (M) is preferably prepared immediately before step (II).

[0043] In step (II), the temperature when the mixture (M) and the isocyanate group-terminated urethane prepolymer (a1) are mixed and stirred to carry out the polymerization reaction is preferably 80°C or lower, more preferably 15 to 40°C. The peripheral speed is preferably 10 to 40 m / s, more preferably 15 to 25 m / s. The mixing time is preferably 30 seconds to 5 minutes. The temperature of the isocyanate group-terminated urethane prepolymer (a1) is preferably 50 to 80°C, and the temperature of the mixture (M) is preferably 10 to 40°C. Within these ranges, the formation and coalescence of primary particles and the severance of the coalesced particles by shear force are repeated during the polymerization reaction, and as the polymerization reaction progresses, the proportion of coalesced particles increases, ultimately resulting in particles with an uneven surface and a sharp particle size distribution.

[0044] The mixing and stirring device is not particularly limited as long as it is a commercially available emulsifier or disperser, and examples thereof include batch-type emulsifiers such as Homogenizer (manufactured by IKA Corporation), Polytron (manufactured by Kinematica Corporation), and TK Auto Homo Mixer (manufactured by Primix Corporation), Ebara Milder (manufactured by Ebara Corporation), TK Filmix, TK Pipeline Homo Mixer (manufactured by Primix Corporation), Colloid Mill (manufactured by Kobe Steel Pantech Co., Ltd.), Slasher, Trigonal Wet Fine Powder Disperser, etc. Examples of such emulsifiers include continuous emulsifiers such as a crusher (manufactured by Mitsui Miike Chemical Engineering Co., Ltd.), Capitron (manufactured by Eurotech), and Fine Flow Mill (manufactured by Pacific Machinery Co., Ltd.), high-pressure emulsifiers such as a Microfluidizer (manufactured by Mizuho Kogyo Co., Ltd.), Nanomizer (manufactured by Nanomizer Co., Ltd.), and APV Gaulin (manufactured by Gaulin), membrane emulsifiers such as a membrane emulsifier (manufactured by Reika Kogyo Co., Ltd.), vibration emulsifiers such as a Vibromixer (manufactured by Reika Kogyo Co., Ltd.), and ultrasonic emulsifiers such as an ultrasonic homogenizer (manufactured by Branson). Of these, preferred ones from the viewpoint of particle size distribution include APV Gaulin, homogenizers, TK Auto Homomixer, Ebara Milder, TK Filmix, and TK Pipeline Homomixer.

[0045] After the thermoplastic polyurethane resin particles (A) are produced, the solvent is removed and solid-liquid separation is performed. As a method for solid-liquid separation, a known method such as centrifugation, belt press, or filter press can be applied. Further, by drying by a known method, the thermoplastic polyurethane resin particles (A) can be obtained.

[0046] The weight-average molecular weight of the thermoplastic polyurethane resin particles (A) is preferably 60,000 to 150,000. When the weight-average molecular weight of the thermoplastic polyurethane resin particles (A) is within this range, it becomes easier to achieve both the meltability of the resin particle composition for DTF printing, the durability of the resulting printed surface, and the texture of the molded product. The weight-average molecular weight of the thermoplastic polyurethane resin particles (A) can be measured using gel permeation chromatography.

[0047] <Plasticizer (B)> The resin particle composition for DTF printing of the present invention contains a plasticizer (B). Because it contains the plasticizer (B) and the fine particles (C) described below, the resin particle composition for DTF printing of the present invention exhibits hydrophobicity. If the resin particle composition for DTF printing is highly hydrophilic, when aqueous ink is used, it will absorb part of the ink that constitutes the image printed by inkjet printing, and if the resin particles slide off the image, a highly accurate transferred image will not be obtained.

[0048] The plasticizer (B) is not particularly limited, and known plasticizers can be used, for example, hydrocarbons, esters of aliphatic or aromatic carboxylic acids [esters of aromatic carboxylic acids and alcohols (e.g., phthalates and trimellitates), and esters of aliphatic carboxylic acids and alcohols (e.g., adipates and sebacates)], fatty acids, hydrogenated products of unsaturated fatty acids, fatty acid esters, and phosphate triesters.

[0049] Among these, from the viewpoint of affinity with the thermoplastic polyurethane resin particles (A), the plasticizer (B) is preferably an ester of an aromatic carboxylic acid, and more preferably a compound represented by the following general formula (1): １ -COO-(EO)n-CO-R ２ (1) In the general formula (1), R １ and R２ represents a benzene ring, EO represents an oxyethylene group, and n represents the average number of moles added, which is a number of 3 to 20, preferably 3 to 12.

[0050] The compound represented by general formula (1) can be obtained by esterifying diol (d) with benzoic acid using a known method. Diol (d) is a diol obtained by adding ethylene oxide to a dihydric alcohol having two carbon atoms, and the number of moles of ethylene oxide added is 3 to 20. Diol (d) is obtained by subjecting ethylene oxide to a dihydric alcohol having two carbon atoms through a ring-opening addition reaction using a known method. From the viewpoints of plasticity and viscosity, the dihydric alcohol having two carbon atoms is preferably an alkylene glycol having two carbon atoms, and specifically, ethylene glycol. The number of moles of ethylene oxide added is 3 to 20, preferably 3 to 12.

[0051] In the esterification reaction, diol (d), benzoic acid, an esterification catalyst, and, if necessary, a solvent are charged into a reactor, and the esterification reaction is carried out by heating while flowing nitrogen through the liquid and removing the generated water from the system, thereby synthesizing a dibenzoate ester. The amount of benzoic acid used in the compound represented by general formula (1) is preferably 2.00 to 2.20 mol, more preferably 2.00 to 2.10 mol, and even more preferably 2.00 to 2.05 mol, per mol of diol (d).

[0052] Examples of the esterification catalyst used in the method for producing the compound represented by general formula (1) include potassium titanium oxalate, sodium titanium oxalate, lithium titanium oxalate, and mixtures thereof. From the viewpoint of low coloration, the content of the esterification catalyst used in the method for producing the compound represented by general formula (1) is preferably 0.000001 to 10 mol %, more preferably 0.000001 to 1 mol %, and even more preferably 0.01 to 1.0 mol %, relative to the total number of carboxyl groups in benzoic acid.

[0053] From the viewpoint of reducing the energy required to distill off the solvent from the reaction apparatus after the esterification step, it is more preferable to use a solvent having a boiling point of 90 to 150° C. Examples of solvents having a boiling point of 90 to 150° C. include saturated aliphatic hydrocarbons such as 2,2,4-trimethylpentane, n-heptane, n-octane, isooctane, nonane, and decane, alicyclic hydrocarbons such as methylcyclohexane, ethylcyclohexane, cycloheptane, and methylcycloheptane, aromatic hydrocarbons such as toluene, ethylbenzene, propylbenzene, butylbenzene, and xylene, and ketone compounds such as methyl propyl ketone, methyl isopropyl ketone (MIPK), methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetylacetone, and 2-cyclohexen-1-one.

[0054] The temperature range during the heating is preferably 120 to 230° C., more preferably 180 to 220° C. The reaction time is preferably 6 to 30 hours, more preferably 7 to 25 hours, and even more preferably 8 to 20 hours.

[0055] In the resin particle composition for DTF printing of the present invention, the content of plasticizer (B) is 5 to 60 wt % based on the weight of the thermoplastic polyurethane resin particles (A). If the content of plasticizer (B) is less than 5 wt % based on the weight of the thermoplastic polyurethane resin particles (A), the meltability of the resin particle composition for DTF printing decreases, while if it exceeds 60 wt %, the durability of the printed surface obtained from the resin particle composition for DTF printing decreases, and the rub fastness (wet conditions) deteriorates. From the viewpoint of achieving both meltability and durability of the printed surface, the content of plasticizer (B) is preferably 10 to 60 wt % based on the weight of the thermoplastic polyurethane resin particles (A), more preferably 25 to 55 wt %, and even more preferably 30 to 50 wt %.

[0056] The content of the plasticizer (B) may be 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, or 50% by weight or more, based on the weight of the thermoplastic polyurethane resin particles (A). The content of the plasticizer (B) may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less, based on the weight of the thermoplastic polyurethane resin particles (A).

[0057] <Fine Particles (C)> The resin particle composition for DTF printing of the present invention contains fine particles (C) that are different from the thermoplastic polyurethane resin particles (A). The fine particles (C) have a composition different from that of the thermoplastic polyurethane resin particles (A) and an average particle diameter smaller than that of the thermoplastic polyurethane resin particles (A).

[0058] The volume average particle diameter of the fine particles (C) in the present invention is preferably 0.1 to 10 μm. If the volume average particle diameter of the fine particles (C) is less than 0.1 μm, powdering will become severe, which may deteriorate operability during DTF printing and the texture of the printed surface. If it exceeds 10 μm, the transfer accuracy during DTF printing may decrease and the melting properties may decrease. From the viewpoint of achieving a balance between operability, transfer accuracy, melting properties, and the texture of the printed surface, the volume average particle diameter of the fine particles (C) is preferably 1.0 to 7.0 μm, and more preferably 2.0 to 6.5 μm.

[0059] The volume average particle diameter of the fine particles (C) is measured using a laser diffraction particle size distribution analyzer (MicrotracMT3000II manufactured by Nikkiso Co., Ltd.) The particle diameter (d50) at which the cumulative amount is 50% in the obtained relative cumulative particle size distribution curve is defined as the volume average particle diameter.

[0060] As the fine particles (C), inorganic fine particles (C1) and / or organic fine particles (C2) can be used. Examples of the inorganic fine particles (C1) include kaolin, talc, silica, titanium oxide, calcium carbonate, bentonite, mica, sericite, glass flakes, glass fiber, graphite, magnesium hydroxide, aluminum hydroxide, antimony trioxide, barium sulfate, zinc borate, condensed aluminum phosphate, alumina, magnesia, wollastonite, xonotlite, whiskers, and metal powder. Examples of the organic fine particles (C2) include those made of vinyl resin, polyester resin, polyurethane resin, epoxy resin, polyamide resin, and polyimide resin. Two or more types of fine particles (C) may be used in combination.

[0061] Among these, from the viewpoint of achieving a balance between the surface hydrophobicity, transfer accuracy, melting properties, and texture of the printed surface of the resin particle composition for DTF printing, it is preferred that the fine particles (C) are one or more types selected from the group consisting of silica, copolymers of alkyl(meth)acrylate and poly(meth)acrylate of polyhydric alcohol, and maleimide copolymers.

[0062] Examples of alkyl(meth)acrylates include alkyl(meth)acrylates having an alkyl group having 1 to 50 carbon atoms, such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, dodecyl(meth)acrylate, hexadecyl(meth)acrylate, heptadecyl(meth)acrylate, eicosyl(meth)acrylate, etc. Examples of polyhydric alcohol poly(meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butylene di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyethylene glycol di(meth)acrylate, etc.

[0063] The maleimide copolymer is preferably one having a crosslinked structure, and more preferably one in which a copolymer of N-cyclohexylmaleimide and 2-hydroxyethyl (meth)acrylate is crosslinked with hexamethylene diisocyanate and / or isophorone diisocyanate.

[0064] In the resin particle composition for DTF printing of the present invention, the content of the fine particles (C) is 0.1 to 10 wt % based on the weight of the thermoplastic polyurethane resin particles (A). If the content of the fine particles (C) is less than 0.1 wt % based on the weight of the thermoplastic polyurethane resin particles (A), it is difficult to obtain a uniform printed surface, and if it exceeds 10 wt %, powdering becomes severe, deteriorating operability during DTF printing and meltability. From the viewpoints of uniformity, operability, and meltability, the content of the fine particles (C) is more preferably 0.3 to 5.0 wt % based on the weight of the thermoplastic polyurethane resin particles (A).

[0065] The content of the fine particles (C) may be 0.1 wt% or more, 0.3 wt% or more, 1.0 wt% or more, 3.0 wt% or more, or 5.0 wt% or more based on the weight of the thermoplastic polyurethane resin particles (A), and the content of the fine particles (C) may be 10 wt% or less, 5.0 wt% or less, 3.0 wt% or less, 1.0 wt% or less, or 0.3 wt% or less based on the weight of the thermoplastic polyurethane resin particles (A).

[0066] The resin particle composition for DTF printing of the present invention may contain additives other than the thermoplastic polyurethane resin particles (A), the plasticizer (B), and the fine particles (C), as necessary. Examples of the additives include antioxidants, hydrophobicity adjusters, and pigments.

[0067] As the antioxidant, known antioxidants can be used, such as phenol-based antioxidants (2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, etc.), bisphenol-based antioxidants (2,2'-methylenebis(4-methyl-6-t-butylphenol) etc.), and phosphorus-based antioxidants (triphenyl phosphite, diphenyl isodecyl phosphite, etc.).

[0068] As the hydrophobicity adjuster, known hydrophobicity adjusters can be used, and examples thereof include fluorine-based hydrophobicity adjusters (such as fluoroalkyl phosphate esters) and silicon-based hydrophobicity adjusters (such as dimethylpolysiloxane, amino-modified dimethylpolysiloxane, carboxyl-modified dimethylpolysiloxane, and ether-modified dimethylpolysiloxane).

[0069] The pigment is not particularly limited, and known organic pigments and / or inorganic pigments can be used.

[0070] Examples of organic pigments include insoluble or soluble azo pigments, copper phthalocyanine pigments, and quinacridone pigments.

[0071] Examples of inorganic pigments include chromates, ferrocyanide compounds, metal oxides (titanium oxide, iron oxide, zinc oxide, aluminum oxide, etc.), metal salts [sulfates (barium sulfate, etc.), silicates (calcium silicate, magnesium silicate, etc.), carbonates (calcium carbonate, magnesium carbonate, etc.), phosphates (calcium phosphate, magnesium phosphate, etc.)], metal powders (aluminum powder, iron powder, nickel powder, copper powder, etc.), and carbon black.

[0072] <Resin Particle Composition for DTF Printing> The resin particle composition for DTF printing of the present invention contains thermoplastic polyurethane resin particles (A), a plasticizer (B), fine particles (C), and other additives as required.

[0073] A variety of fabrics are used in DTF printing. However, polyester fabrics have lower heat resistance than cotton fabrics, so a thermoplastic resin with a low flow initiation temperature must be used and melted and transferred at a lower temperature. The white urethane powder described in Patent Document 1 is said to have a flow initiation temperature of 115°C, which allows it to melt at a relatively low temperature and transfer without damaging polyester fabrics. However, when using a thermoplastic resin with such a low flow initiation temperature, the molten thermoplastic resin penetrates into the fabric during transfer, leaving the shape of the fabric on the transfer surface, resulting in a deterioration of the texture. Therefore, it is preferable to achieve both transfer meltability and texture without limiting the fabric to be transferred.

[0074] From the above viewpoints, the resin particle composition for DTF printing of the present invention preferably has a flow initiation temperature measured with a flow tester of 135 to 175° C. If the flow initiation temperature is less than 135° C., the texture may deteriorate during DTF printing. If the temperature exceeds 175° C., the transfer melting property during DTF printing may decrease.

[0075] The resin particle composition for DTF printing of the present invention has a flow rate of 1.0×10 at 170° C. as measured by a flow tester for the resin particle composition. －３ cm ３ In terms of transfer melting property, it is preferable that the flow rate at 170°C is 5.0 x 10 / s or more. －３ cm ３ / s or less is preferable from the viewpoint of texture of the transferred surface.

[0076] The flow initiation temperature and flow rate of the resin particle composition measured with a flow tester can be measured, for example, using a flow tester [Shimadzu Corporation's "Capillary Tube Rheometer CFT-500D"] under the following conditions: <Measurement conditions> Starting temperature (°C): 80 Heating rate (°C / min): 5.0 Preheating time (s): 300 Test force (kgf): 5 Die hole diameter (mm): 0.5 Die length (mm): 10 Sample amount (g): 1.5

[0077] The resin particle composition for DTF printing of the present invention can be produced by mixing thermoplastic polyurethane resin particles (A), plasticizer (B), fine particles (C), and other additives as necessary. While there are no particular limitations on the order of mixing, it is preferable to first mix the thermoplastic polyurethane resin particles (A) and plasticizer (B), impregnate the thermoplastic polyurethane resin particles (A) with the plasticizer (B), and then add and mix the fine particles (C). The impregnation of the thermoplastic polyurethane resin particles (A) with the plasticizer (B) is preferably carried out by heating at 40 to 90°C for at least 1 hour. From the viewpoint of production process efficiency, the heating time is preferably 72 hours or less, more preferably 8 hours or less, and particularly preferably 5 hours or less.

[0078] As the mixer, any known powder mixer can be used, including a container rotation type mixer, a fixed container type mixer, and a fluid motion type mixer. For example, fixed container type mixers include high-speed fluid mixers, double-shaft paddle type mixers, high-speed shear mixers (Hensiel Mixer (registered trademark), etc.), low-speed mixers (planetary mixers, etc.), and conical screw mixers (Nauta Mixer (registered trademark, omitted below) and the like). Among these, double-shaft paddle type mixers, low-speed mixers (planetary mixers, etc.), and conical screw mixers (Nauta Mixer, etc.) are preferred.

[0079] The present specification discloses the following:

[0080] Disclosure <1-1> is a resin particle composition for DTF printing containing thermoplastic polyurethane resin particles (A), a plasticizer (B), and fine particles (C) different from the thermoplastic polyurethane resin particles (A), wherein the content of the plasticizer (B) is 5 to 60 wt % based on the weight of the thermoplastic polyurethane resin particles (A), and the content of the fine particles (C) is 0.1 to 10 wt % based on the weight of the thermoplastic polyurethane resin particles (A).

[0081] The present disclosure <1-2> is the resin particle composition for DTF printing according to the present disclosure <1-1>, wherein the resin particle composition has a flow initiation temperature of 135 to 175°C as measured with a flow tester.

[0082] The present disclosure <1-3> is a resin particle composition having a flow rate of 1.0 × 10 at 170 ° C. measured with a flow tester. －３ cm ３ / s or more.

[0083] The present disclosure <1-4> is the resin particle composition for DTF printing according to any one of the present disclosures <1-1> to <1-3>, wherein the thermoplastic polyurethane resin particles (A) have a volume average particle diameter of 100 to 300 μm.

[0084] The present disclosure <1-5> is the resin particle composition for DTF printing according to any one of the present disclosures <1-1> to <1-4>, wherein the fine particles (C) have a volume average particle diameter of 0.1 to 10 μm.

[0085] The present disclosure <1-6> is the resin particle composition for DTF printing according to any one of the present disclosures <1-1> to <1-5>, wherein the thermoplastic polyurethane resin particles (A) are a thermoplastic polyurethane resin obtained by reacting an aliphatic diisocyanate (a1-1), a monool (a1-2), a diol (a1-3) having a number average molecular weight of 500 to 10,000, and an amine (a2).

[0086] The present disclosure <1-7> relates to the resin particle composition for DTF printing according to the present disclosure <1-6>, wherein the amine (a2) is an alicyclic diamine and / or an aliphatic diamine.

[0087] The present disclosure <1-8> is the resin particle composition for DTF printing according to any one of the present disclosures <1-1> to <1-7>, wherein the plasticizer (B) is a compound represented by the following general formula (1): １ -COO-(EO)n-CO-R ２ (1) (In general formula (1), R １ and R ２ represents a benzene ring, EO represents an oxyethylene group, and n represents the average number of moles added, which is a number from 3 to 20.

[0088] The present disclosure <1-9> is the resin particle composition for DTF printing according to any one of the present disclosures <1-1> to <1-8>, wherein the fine particles (C) are at least one selected from the group consisting of silica, a copolymer of an alkyl(meth)acrylate and a poly(meth)acrylate of a polyhydric alcohol, and a maleimide copolymer.

[0089] Disclosure <1-10> is a method for producing a resin particle composition for DTF printing, which contains thermoplastic polyurethane resin particles (A), a plasticizer (B), and fine particles (C) different from the thermoplastic polyurethane resin particles (A), wherein the thermoplastic polyurethane resin particles (A) are made of a thermoplastic polyurethane resin obtained by reacting an isocyanate group-terminated urethane prepolymer (a1) with an amine (a2), the content of the plasticizer (B) is 5 to 60 wt % based on the weight of the thermoplastic polyurethane resin particles (A), and the content of the fine particles (C) is 0.1 to 10 wt % based on the weight of the thermoplastic polyurethane resin particles (A), and the method for producing a resin particle composition for DTF printing includes a step of mixing and stirring a mixture (M) containing the amine (a2), an organic solvent (K) having a relative dielectric constant of 5 to 25, and water with the isocyanate group-terminated urethane prepolymer (a1) to obtain the thermoplastic polyurethane resin particles (A).

[0090] The present disclosure <1-11> is a method for producing a resin particle composition for DTF printing according to the present disclosure <1-10>, comprising a step of reacting an aliphatic diisocyanate (a1-1), a monool (a1-2), and a diol (a1-3) having a number average molecular weight of 500 to 10,000 to obtain the isocyanate group-terminated urethane prepolymer (a1).

[0091] The present disclosure <1-12> is the method for producing a resin particle composition for DTF printing according to the present disclosure <1-10> or <1-11>, wherein the equivalent amount of the amine (a2) is 0.70 to 1.00 equivalents per equivalent of the isocyanate group of the isocyanate group-terminated urethane prepolymer (a1).

[0092] The present disclosure <1-13> is the method for producing a resin particle composition for DTF printing according to any one of the present disclosures <1-10> to <1-12>, wherein the content of the organic solvent (K) is 5 to 30 wt % based on the total weight of the mixture (M) and the isocyanate group-terminated urethane prepolymer (a1).

[0093] The present disclosure <1-14> is a method for producing a resin particle composition for DTF printing according to any one of the present disclosures <1-10> to <1-13>, comprising a step of mixing the thermoplastic polyurethane resin particles (A) and the plasticizer (B) and heating the mixture at 40 to 90°C for 1 hour or longer to impregnate the thermoplastic polyurethane resin particles (A) with the plasticizer (B).

[0094] The present disclosure <2-1> is a resin particle composition for DTF printing, which contains thermoplastic polyurethane resin particles (A) having a volume average particle diameter of 100 to 300 μm, a plasticizer (B), and inorganic fine particles (C1) or organic fine particles (C2) having a volume average particle diameter of 0.1 to 10 μm, wherein the thermoplastic polyurethane resin particles (A) are aliphatic diisocyanate (a1-1), monool (a1-2), diol (a1-3) having a number average molecular weight of 500 to 10,000, and amine and (a2), the content of the plasticizer (B) is 10 to 60% by weight based on the weight of the thermoplastic polyurethane resin particles (A), the content of the inorganic fine particles (C1) or the organic fine particles (C2) is 0.1 to 10% by weight based on the weight of the thermoplastic polyurethane resin particles (A), and the resin particle composition has a flow initiation temperature of 135 to 155°C as measured with a flow tester.

[0095] The present disclosure <2-2> is a resin particle composition having a flow rate of 1.0 × 10 at 170 ° C. measured with a flow tester. －３ cm ３ / s or more.

[0096] The present disclosure <2-3> relates to the resin particle composition for DTF printing according to the present disclosure <2-1> or <2-2>, wherein the plasticizer (B) is a compound represented by the following general formula (1): １ -COO-(EO)n-CO-R ２ (1) (In general formula (1), R １ and R ２ represents a benzene ring, EO represents an oxyethylene group, and n represents the average number of moles added, which is a number from 3 to 20.

[0097] The present disclosure <2-4> is the resin particle composition for DTF printing according to any one of the present disclosures <2-1> to <2-3>, wherein the inorganic fine particles (C1) are silica, and the organic fine particles (C2) are at least one selected from the group consisting of a copolymer of an alkyl(meth)acrylate and a poly(meth)acrylate of a polyhydric alcohol, and a maleimide copolymer.

[0098] The present disclosure <2-5> is a method for producing a resin particle composition for DTF printing, which contains thermoplastic polyurethane resin particles (A) having a volume average particle diameter of 100 to 300 μm, a plasticizer (B), and inorganic fine particles (C1) or organic fine particles (C2) having a volume average particle diameter of 0.1 to 10 μm, wherein the thermoplastic polyurethane resin particles (A) are made of a thermoplastic polyurethane resin obtained by reacting an isocyanate group-terminated urethane prepolymer (a1) obtained by reacting an aliphatic diisocyanate (a1-1), a monool (a1-2), and a diol (a1-3) having a number average molecular weight of 500 to 10,000 with an amine (a2), and the content of the plasticizer (B) is a step of mixing and stirring a mixture (M) containing an amine (a2), an organic solvent (K) having a relative dielectric constant of 5 to 25, and water with an isocyanate group-terminated urethane prepolymer (a1) to obtain thermoplastic polyurethane urea resin particles (A), wherein the content of the inorganic fine particles (C1) or the organic fine particles (C2) is 10 to 60% by weight based on the weight of the thermoplastic polyurethane resin particles (A), and 0.1 to 10% by weight based on the weight of the thermoplastic polyurethane resin particles (A), and the amount of the amine (a2) is such that the equivalent of (a2) is 0.70 to 0.90 equivalents per equivalent of the isocyanate group of the isocyanate group-terminated urethane prepolymer (a1).

[0099] Disclosure <3-1> is a resin particle composition for DTF printing, containing thermoplastic polyurethane resin particles (A) having a volume average particle diameter of 100 to 300 μm, a plasticizer (B), and inorganic or organic fine particles (C) having a volume average particle diameter of 0.1 to 10 μm, in which the thermoplastic polyurethane resin particles (A) are made of a thermoplastic polyurethane resin obtained by reacting an aliphatic diisocyanate (a1-1), a monool (a1-2), a diol (a1-3) having a number average molecular weight of 500 to 10,000, and an alicyclic diamine and / or an aliphatic diamine (a2), the content of the plasticizer (B) is 10 to 60 wt % based on the weight of the thermoplastic polyurethane resin particles (A), and the content of the inorganic or organic fine particles (C) is 0.1 to 10 wt % based on the weight of the thermoplastic polyurethane resin particles (A).

[0100] The present disclosure <3-2> is the resin particle composition for DTF printing according to the present disclosure <3-1>, wherein the plasticizer (B) is a compound represented by the following general formula (1): １ -COO-(EO)n-CO-R ２ (1) (In general formula (1), R １ and R ２ represents a benzene ring, EO represents an oxyethylene group, and n represents the average number of moles added, which is a number from 4 to 20.

[0101] The present disclosure <3-3> is the resin particle composition for DTF printing according to the present disclosure <3-1> or <3-2>, wherein the inorganic or organic fine particles (C) are at least one selected from the group consisting of silica, a copolymer of an alkyl(meth)acrylate and a poly(meth)acrylate of a polyhydric alcohol, and a maleimide copolymer.

[0102] The present disclosure <3-4> is a method for producing a resin particle composition for DTF printing, which contains thermoplastic polyurethane resin particles (A) having a volume average particle diameter of 100 to 300 μm, a plasticizer (B), and inorganic or organic fine particles (C) having a volume average particle diameter of 0.1 to 10 μm, wherein the thermoplastic polyurethane resin particles (A) are made of a thermoplastic polyurethane resin obtained by reacting an isocyanate group-terminated urethane prepolymer (a1) obtained by reacting an aliphatic diisocyanate (a1-1), a monool (a1-2), and a diol (a1-3) having a number average molecular weight of 500 to 10,000 with an alicyclic diamine and / or an aliphatic diamine (a2), and the content of the plasticizer (B) is a process for producing a resin particle composition for DTF printing, the process comprising: a step of mixing and stirring a mixture (M) containing an alicyclic diamine and / or an aliphatic diamine (a2), an organic solvent (K) having a relative dielectric constant of 5 to 25, and water with an isocyanate group-terminated urethane prepolymer (a1) to obtain thermoplastic polyurethane urea resin particles (A), the content of said inorganic or organic fine particles (C) being 10 to 60% by weight based on the weight of the thermoplastic polyurethane resin particles (A); and 0.1 to 10% by weight based on the weight of the thermoplastic polyurethane resin particles (A), the process comprising: mixing and stirring a mixture (M) containing an alicyclic diamine and / or an aliphatic diamine (a2), an organic solvent (K) having a relative dielectric constant of 5 to 25, and water with an isocyanate group-terminated urethane prepolymer (a1), the content of said (K) in the process being 5 to 30% by weight based on the total weight of the mixture (M) and the isocyanate group-terminated urethane prepolymer (a1).

[0103] The present disclosure <3-5> is the method for producing a resin particle composition for DTF printing according to the present disclosure <3-4>, further comprising a step of mixing the thermoplastic polyurethane resin particles (A) and the plasticizer (B) and heating the mixture at 40 to 90°C for 1 hour or more to impregnate the thermoplastic polyurethane resin particles (A) with the plasticizer (B).

[0104] The present invention will be further explained below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" below refer to parts by weight.

[0105] <Production Example 1> [Production of Thermoplastic Polyurethane Resin Particles (A-1)] A reaction vessel equipped with a thermometer, a stirrer, and a nitrogen inlet tube was charged with 282.9 parts of polyethylene isophthalate having an Mn of 2,300 as the polyester diol (a1-3), 424.4 parts of polybutylene adipate having an Mn of 1,000 as the polyester diol (a1-3), 9.34 parts of benzyl alcohol as the monool (a1-2), and 5.88 parts of 1,4-butanediol as a chain extender, and after nitrogen substitution, the mixture was heated to 110°C with stirring to melt, and then cooled to 50°C. Subsequently, 150.0 parts of methyl ethyl ketone as an organic solvent and 132.0 parts of hexamethylene diisocyanate as the aliphatic diisocyanate (a1-1) were added, and the mixture was reacted at 90°C for 6 hours. After cooling to 70°C, 1.4 parts of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added as a stabilizer and mixed uniformly to obtain a solution of isocyanate-terminated urethane prepolymer (a1). The isocyanate group content of the resulting prepolymer solution was 1.63%. Subsequently, in a reaction vessel, 157.9 parts of an aqueous solution of 5.9 parts of Sunspearl PS-8 [polycarboxylic acid type anionic surfactant manufactured by Sanyo Chemical Industries, Ltd.] dissolved in 152 parts of water as a dispersion stabilizer and 37.1 parts of methyl ethyl ketone as an organic solvent (K) (14 wt.% based on the total weight of the mixture (M) and isocyanate group-terminated urethane prepolymer (a1)) was added and stirred uniformly at 20 ° C., and then 2.2 parts of hexamethylenediamine as the amine (a2) was added and mixed for 1 minute using an Ultra Disperser [manufactured by Yamato Scientific Co., Ltd.] at a peripheral speed of 23 m / s (rotation speed: 10,000 rpm). Subsequently, 103.3 parts of the solution of prepolymer (a1) adjusted to 75 ° C. was added, and the peripheral speed was 23 m / s, and the mixture was mixed at 40 ° C. or less for 2 minutes. The mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen inlet tube. Thereafter, the solvent was removed under reduced pressure while stirring at 40° C. for 2 hours, and then at 80° C. for 2 hours. After the reaction was completed, the mixture was filtered and dried, and those that passed through a sieve with an opening of 425 μm were obtained as thermoplastic polyurethane resin particles (A-1).

[0106] Production Example 2 Production of Thermoplastic Polyurethane Resin Particles (A-2) Thermoplastic polyurethane resin particles (A-1) were spread to a thickness of 1 mm on a mold heated to 230°C and melted, and after 1 minute, the particles were water-cooled and demolded from the mold to obtain a thermoplastic polyurethane resin molded product. This molded product was freeze-pulverized using a freeze-pulverizer "PULVERISETTE 14" (manufactured by FRITSCH, 20,000 rpm, 8 stainless steel blades, heavy-duty sieve ring 0.75 mm), and the particles passed through a sieve with 425 μm openings were used as thermoplastic polyurethane resin particles (A-2).

[0107] <Production Example 3> [Production of Thermoplastic Polyurethane Resin Particles (A-3)] A reaction vessel equipped with a thermometer, a stirrer, and a nitrogen inlet tube was charged with 282.9 parts of polyethylene isophthalate having an Mn of 2,300 as the polyester diol (a1-3), 424.4 parts of polybutylene adipate having an Mn of 1,000 as the polyester diol (a1-3), 9.34 parts of benzyl alcohol as the monool (a1-2), and 5.88 parts of 1,4-butanediol as a chain extender, and after nitrogen substitution, the mixture was heated to 110°C with stirring to melt, and then cooled to 50°C. Subsequently, 150.0 parts of methyl ethyl ketone as an organic solvent and 132.0 parts of hexamethylene diisocyanate as the aliphatic diisocyanate (a1-1) were added, and the mixture was allowed to react at 90°C for 6 hours. Next, after cooling to 70 ° C., 1.4 parts of Irganox 1010 [manufactured by Ciba Specialty Chemicals Co., Ltd.] as a stabilizer was added and mixed uniformly to obtain a solution of isocyanate group-terminated urethane prepolymer (a1). The isocyanate group content of the obtained prepolymer solution was 1.63%. Subsequently, 157.9 parts of an aqueous solution obtained by dissolving 5.9 parts of Sunspearl PS-8 [manufactured by Sanyo Chemical Industries, Ltd.] as a dispersion stabilizer in 152 parts of water and 37.1 parts of methyl ethyl ketone as an organic solvent (K) were added to a reaction vessel and stirred uniformly at 20 ° C., and then 1.8 parts of hexamethylenediamine as an amine (a2) was added and mixed for 1 minute using an Ultra Disperser [manufactured by Yamato Scientific Co., Ltd.] at a peripheral speed of 23 m / s (rotation speed: 10,000 rpm). Subsequently, 103.3 parts of a solution of prepolymer (a1) adjusted to 75°C was added, and after mixing at a peripheral speed of 23 m / s and 40°C or less for 2 minutes, the mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen inlet tube. Thereafter, the solvent was removed at 40°C for 2 hours with stirring under reduced pressure, and then at 80°C for 2 hours. After completion of the reaction, the mixture was filtered and dried, and those that passed through a sieve with 425µm openings were obtained as thermoplastic polyurethane resin particles (A-3).

[0108] <Thermoplastic polyurethane resin particles (comparison A-1)> A commercially available TPU powder for DTF printing, "U-1" (manufactured by Ecofreen Co., Ltd.), was used as is as the thermoplastic polyurethane resin particles (comparison A-1). The product was analyzed using a surface IR "FTIR-8400" (manufactured by Shimadzu Corporation), and it was confirmed that the product was made of a polycarbonate-based urethane resin.

[0109] Example 1 Production of Resin Particle Composition (P-1) for DTF Printing In a planetary mixer (PRIMIX, Model Hibismix 2P-03), 100 parts of thermoplastic polyurethane resin particles (A-1) and 10 parts of polyethylene glycol dibenzoate (Sunflex EB-300Y, manufactured by Sanyo Chemical Industries, Ltd.) serving as a plasticizer were added and mixed at 100 rpm for 3 minutes. The mixture was then transferred to a thermostatic oven at 80°C and heated for 2 hours. After cooling to room temperature, 1.0 part of crosslinked polymethyl methacrylate (Ganzpearl PM-030S, average particle size approximately 3-5 μm, manufactured by AICA Kogyo Co., Ltd.) serving as a flow improver (organic fine particles) was added and mixed at 100 rpm for 1 minute. The mixture was passed through a sieve with 425 μm openings to obtain a resin particle composition (P-1) for DTF printing.

[0110] Examples 2 to 6 Production of Resin Particle Compositions (P-2) to (P-6) for DTF Printing Resin particle compositions (P-2) to (P-6) for DTF printing were obtained in the same manner as in Example 1, except that the amounts of raw materials charged were changed to the blends shown in Table 1.

[0111] Example 7 Production of Resin Particle Composition for DTF Printing (P-7) 100 parts of thermoplastic polyurethane resin particles (A-1), 30 parts of polyethylene glycol dibenzoate (Sunflex EB-300Y, manufactured by Sanyo Chemical Industries, Ltd.) as a plasticizer, and 0.25 parts of dimethylpolysiloxane (L45-1000, manufactured by Toray Dow Corning Co., Ltd.) as a hydrophobicity adjuster were charged into a planetary kneader (Hibismix 2P-03, manufactured by Primix Corporation), and the mixture was mixed at 100 rpm for 3 minutes, and then transferred to a constant temperature dryer at 80°C and heated for 2 hours. After cooling to room temperature, 1.0 part of crosslinked polymethyl methacrylate [Ganzpearl PM-030S, manufactured by AICA Kogyo Co., Ltd.] serving as a flowability improver (organic fine particles) was added using a planetary mixer, and the mixture was mixed at 100 rpm for 1 minute. The mixture was passed through a sieve with 425 μm openings, and this was used as a resin particle composition for DTF printing (P-7).

[0112] Examples 8 to 9 Production of Resin Particle Compositions (P-8) to (P-9) for DTF Printing Resin particle compositions (P-8) to (P-9) for DTF printing were obtained in the same manner as in Example 7, except that the amounts of raw materials charged were changed to the blends shown in Tables 1 and 2.

[0113] Example 10 Production of Resin Particle Composition for DTF Printing (P-10) A resin particle composition for DTF printing (P-10) was obtained in the same manner as in Example 9, except that polyethylene glycol dibenzoate (Sunflex EB-200Y, manufactured by Sanyo Chemical Industries, Ltd.) was used as the plasticizer.

[0114] Example 11 Production of Resin Particle Composition (P-11) for DTF Printing A resin particle composition (P-11) for DTF printing was obtained in the same manner as in Example 7, except that 100 parts of thermoplastic polyurethane resin particles (A-2) were used as the thermoplastic polyurethane resin particles and the amount of plasticizer was changed to 40 parts.

[0115] Example 12 Production of Resin Particle Composition for DTF Printing (P-12) 100 parts of thermoplastic polyurethane resin particles (A-3), 5 parts of polyethylene glycol dibenzoate (Sunflex EB-200Y, manufactured by Sanyo Chemical Industries, Ltd.) as a plasticizer, and 0.50 parts of dimethylpolysiloxane (L45-1000, manufactured by Toray Dow Corning Co., Ltd.) as a hydrophobicity adjuster were charged into a planetary kneader (Hibismix 2P-03, manufactured by Primix Corporation), and the mixture was mixed at 100 rpm for 3 minutes, and then transferred to a constant temperature dryer at 80°C and heated for 2 hours. After cooling to room temperature, 1.0 part of crosslinked polymethyl methacrylate [Ganzpearl PM-030S, manufactured by AICA Kogyo Co., Ltd.] serving as a flowability improver (organic fine particles) was added using a planetary mixer, and the mixture was mixed at 100 rpm for 1 minute. The mixture was passed through a sieve with 425 μm openings, and this was used as a resin particle composition for DTF printing (P-12).

[0116] Examples 13 to 15 Production of Resin Particle Compositions (P-13) to (P-15) for DTF Printing Resin particle compositions (P-13) to (P-15) for DTF printing were obtained in the same manner as in Example 12, except that the amounts of raw materials charged were changed to the blends shown in Table 2.

[0117] Example 16 Production of Resin Particle Composition for DTF Printing (P-16) A resin particle composition for DTF printing (P-16) was obtained in the same manner as in Example 12, except that 60 parts of polyethylene glycol dibenzoate (Sunflex EB-300Y, manufactured by Sanyo Chemical Industries, Ltd.) was used as the plasticizer.

[0118] Comparative Examples 1 to 6 [Production of Resin Particle Compositions for DTF Printing (Comparative P-1) to (Comparative P-6)] Resin particle compositions for DTF printing (Comparative P-1) to (Comparative P-6) were obtained in the same manner as in the other Examples, except that the types and amounts of raw materials charged were changed to the formulations shown in Table 3.

[0119] Measurements and evaluations were carried out on the resin particle compositions of each of the Examples and Comparative Examples, and the results are shown in Tables 1 to 3.

[0120]

[0121]

[0122]

[0123] <Measurement of Bulk Density> The bulk density (loose bulk density) of the resin particle compositions for DTF printing obtained in each of the Examples and Comparative Examples was measured using a Powder Tester PT-X (manufactured by Hosokawa Micron Corporation). The sample was placed on a circular sieve with a diameter of 7.5 cm and openings of 1.7 mm, with a thickness of 200 to 300 cm. ３ The sample was subjected to free fall from a height of 27 cm, and the sample was dropped onto a 100 cm stainless steel sieve placed below the sieve. ３ The sample was poured into a cup (inner diameter approximately 5 cm x height approximately 5 cm). After pouring the sample into the cup until it overflowed, the vibration of the sieve was stopped. Then, the excess powder sample on the cup was leveled off along the top surface of the cup with a rectangular blade, and the weight (g) of the powder sample in the cup was measured to calculate the loose bulk density using the following formula. The loose bulk density was measured three times for each sample, and the average value was used as the loose bulk density value of that sample. The results are shown in Tables 1 to 3. Loose bulk density (g / cm ３ ) = weight of powder sample in cup (g) / 100 (cm ３ )

[0124] <Preparation of Evaluation Paint> The evaluation paint to be used in each test was prepared as follows: 16.2 parts of polyurethane resin dispersion "Ucoat UWS-145" (manufactured by San Nopco Ltd.), 34.0 parts of carbon black aqueous dispersion "Aqua-Black 162" (manufactured by Tokai Carbon Co., Ltd., solids concentration 20% by weight), 28.8 parts of propylene glycol, 1.9 parts of 1,2-hexanediol, 1.9 parts of 2-pyrrolidone, and 17.2 parts of water were charged into a container and mixed for 10 minutes to prepare the evaluation paint.

[0125] <Evaluation of Water Absorbency: Evaluation of Hydrophobicity> The evaluation paint was applied to a 200 cm x 120 cm area of ​​a DTF transfer film "DTF Premium Film" (manufactured by ECOFREEN) cut to 210 cm x 148 cm using a bar coater (RDS20). The resin particle composition for DTF printing obtained in each Example and Comparative Example was evenly sprayed onto the applied evaluation paint from a 100 mL plastic container so that the entire surface coated with the evaluation paint was covered. The film was tilted 45° to remove excess resin particle composition for DTF printing. This excess resin particle composition for DTF printing was collected and spread on a white paper. The proportion of the resin particle composition for DTF printing colored with the evaluation paint was visually evaluated using a grade system, with grades of 2 and higher (grades 2 to 4) considered acceptable. The fact that the resin particle composition for DTF printing is not colored indicates that it does not absorb the water-based ink (evaluation paint), and indicates that the hydrophobicity of the resin particle composition for DTF printing is sufficiently high. The results are shown in Tables 1 to 3. Grade 4: Almost no colored resin particle composition for DTF printing is observed Grade 3: Colored resin particle composition for DTF printing is observed in about 1% of the total Grade 2: Colored resin particle composition for DTF printing is observed in about 10% of the total Grade 1: Colored resin particle composition for DTF printing is observed in 20% or more of the total

[0126] [Flow Initiation Temperature and Flow Rate at 170°C] Using a flow tester [Shimadzu Corporation's "Capillary Tube Rheometer CFT-500D"], the flow initiation temperature and flow rate at 170°C of the resin particle compositions for DTF printing obtained in each Example and Comparative Example were measured under the following measurement conditions: <Measurement Conditions> Starting temperature (°C): 80 Heating rate (°C / min): 5.0 Preheating time (s): 300 Test force (kgf): 5 Die hole diameter (mm): 0.5 Die length (mm): 10 Sample amount (g): 1.5

[0127] [Transfer Meltability (Polyester Fabric)] The evaluation paint was applied to a 200 cm x 120 cm area of ​​DTF transfer film "DTF Premium Film" (manufactured by ECOFREEN) cut to 210 cm x 148 cm using a bar coater (RDS20). The resin particle composition for DTF printing obtained in each Example and Comparative Example was sprayed evenly from a 100 mL plastic container onto the applied ink so that the entire surface coated with the evaluation paint was covered. The film was then tilted 45° to remove excess resin particle composition for DTF printing. The film was then placed in a dryer "AVO-310V" (manufactured by ASONE) set to 160°C and preheated for 2 minutes. The polyester fabric was placed in a heat press machine "HSP-5400" (manufactured by HASHIMA) set to 130°C and pressed for 60 seconds under a load of 100 kg to preheat the polyester fabric. The film was placed on this polyester fabric and heat-pressed for 10 seconds at 130°C with a load of 100 kg in the same press, thereby transferring the coating from the film to the polyester fabric. After cooling to room temperature, the film was peeled off, and the polyester fabric to which the evaluation coating surface had been transferred was again heat-pressed for 5 seconds at 130°C with a load of 100 kg in the same press. After cooling to room temperature, the transferred surface of the obtained polyester fabric was visually inspected for peeling or chipping, and a grade of 3 or higher (grades 3 and 4) was deemed to be acceptable. The results are shown in Tables 1 to 3. Grade 4: No peeling or chipping Grade 3: Peeling or chipping of less than 1 mm in diameter Grade 2: Peeling or chipping of 1 mm to less than 10 mm in diameter Grade 1: Peeling or chipping of 10 mm or more in diameter

[0128] [Texture of Transfer Surface (Polyester Fabric)] The transfer surface of the polyester fabric prepared for the evaluation of transfer melting property was touched with a finger, and the texture was evaluated as a texture, with grades 2 or higher (grades 2 and 3) being considered acceptable. The results are shown in Tables 1 to 3. Grade 3: No texture of the fabric. Grade 2: Slight texture of the fabric remains. Grade 1: Texture of the fabric remains.

[0129] [Transfer Meltability (Cotton Fabric)] The evaluation paint was applied to a 200 cm x 120 cm area of ​​a DTF transfer film "DTF Premium Film" (manufactured by ECOFREEN) cut to 210 cm x 148 cm using a bar coater (RDS20). The resin particle composition for DTF printing obtained in each Example and Comparative Example was evenly sprayed onto the applied evaluation paint from a 100 mL plastic container so that the entire coating surface of the evaluation paint was covered. The film was then tilted 45° to remove excess resin particle composition for DTF printing. The film was then placed in a dryer "AVO-310V" (manufactured by ASONE) set to 160°C and preheated for 2 minutes. A T-shirt fabric (made of cotton) was placed in a heat press machine "HSP-5400" (manufactured by HASHIMA) set to 160°C and pressed with a load of 100 kg for 60 seconds to preheat the T-shirt fabric. The film was placed on this T-shirt fabric, and the T-shirt fabric was heat-pressed at 160°C with a load of 100 kg for 10 seconds in the same press, thereby transferring the coating from the film to the T-shirt fabric. After cooling to room temperature, the film was peeled off to obtain a T-shirt fabric with the evaluation coating surface transferred thereto. The transferred surface of the obtained T-shirt fabric was visually inspected for peeling or chipping, and a grade of 3 or higher (grades 3 and 4) was deemed acceptable. The results are shown in Tables 1 to 3. Grade 4: No peeling or chipping Grade 3: Peeling or chipping of less than 1 mm in diameter Grade 2: Peeling or chipping of 1 mm to less than 10 mm in diameter Grade 1: Peeling or chipping of 10 mm or more in diameter

[0130] [Feel of Transferred Surface (Cotton Fabric)] The feel of the transferred surface of the polyester fabric was evaluated in the same manner as in the evaluation of the feel of the transferred surface of the polyester fabric, except that the fabric was cotton. The results are shown in Tables 1 to 3.

[0131] <Evaluation of Rubbing Fastness> A rub fastness test was conducted for each of the T-shirt fabrics with the transferred dye prepared for the evaluation of transfer meltability in accordance with JIS L 0849. A 140 mm x 50 mm test piece was cut from the transferred T-shirt fabric to serve as the measurement sample. After attaching the measurement sample to a friction tester "RT200" (manufactured by Daiei Scientific Instruments Co., Ltd.) with double-sided tape, a cotton fabric (No. 3 gold width) was attached to the indenter and rubbed 100 times at a speed of 30 reciprocating strokes per minute over a 100 mm area of ​​the test piece with a load of 2 N. Dry and wet tests were conducted, with the cotton fabric (No. 3 gold width) being dry for the dry test and 100% water-moistened for the wet test. The dye transfer density of the cotton fabric (No. 3 gold width) after the test was measured at nine points using a spectrophotometer "X-rite 938" (manufactured by X-Rite), and the average value was used as the dye transfer density. The dye transfer density was evaluated as a grade according to the following criteria. The higher the grade, the better the rub fastness. Grades 3 and above (grades 3 and 4) under dry conditions and grades 2 and above (grades 2 to 4) under wet conditions were considered acceptable. The results are shown in Tables 1 to 3. Grade 4: 0.00 to 0.10 Grade 3: 0.11 to 0.25 Grade 2: 0.26 to 0.35 Grade 1: 0.36 or above

[0132] The results of each of the Examples and Comparative Examples show that the resin particle compositions for DTF printing of each Example are highly hydrophobic, and the durability (fastness) of the printed images is high.

[0133] The resin particle composition for DTF printing of the present invention can be suitably used as thermoplastic resin particles to be arranged on an image printed during DTF printing, and is also useful as a material for screen printing or inkjet printing directly onto textile products.

Claims

1. A resin particle composition for DTF printing containing thermoplastic polyurethane resin particles (A), a plasticizer (B), and fine particles (C) different from the thermoplastic polyurethane resin particles (A), wherein the content of the plasticizer (B) is 5 to 60% by weight based on the weight of the thermoplastic polyurethane resin particles (A), and the content of the fine particles (C) is 0.1 to 10% by weight based on the weight of the thermoplastic polyurethane resin particles (A).

2. The resin particle composition for DTF printing according to claim 1, wherein the resin particle composition has a flow initiation temperature of 135 to 175°C as measured with a flow tester.

3. The flow rate of the resin particle composition at 170°C measured with a flow tester is 1.0 x 10 －３ cm ３ 3. The resin particle composition for DTF printing according to claim 1, wherein the viscosity is 1 / s or more.

4. A resin particle composition for DTF printing according to claim 1 or 2, wherein the volume average particle diameter of the thermoplastic polyurethane resin particles (A) is 100 to 300 μm.

5. The resin particle composition for DTF printing according to claim 1 or 2, wherein the volume average particle diameter of the fine particles (C) is 0.1 to 10 μm.

6. A resin particle composition for DTF printing according to claim 1 or 2, wherein the thermoplastic polyurethane resin particles (A) are a thermoplastic polyurethane resin obtained by reacting an aliphatic diisocyanate (a1-1), a monool (a1-2), a diol (a1-3) having a number average molecular weight of 500 to 10,000, and an amine (a2).

7. The resin particle composition for DTF printing according to claim 6, wherein the amine (a2) is an alicyclic diamine and / or an aliphatic diamine.

8. The resin particle composition for DTF printing according to claim 1 or 2, wherein the plasticizer (B) is a compound represented by the following general formula (1): １ -COO-(EO)n-CO-R ２ (1) (In general formula (1), R １ and R ２ represents a benzene ring, EO represents an oxyethylene group, and n represents the average number of moles added, which is a number from 3 to 20.

9. A resin particle composition for DTF printing as described in claim 1 or 2, wherein the microparticles (C) are one or more selected from the group consisting of silica, copolymers of alkyl(meth)acrylate and poly(meth)acrylate of polyhydric alcohol, and maleimide copolymers.

10. A method for producing a resin particle composition for DTF printing containing thermoplastic polyurethane resin particles (A), a plasticizer (B), and fine particles (C) different from the thermoplastic polyurethane resin particles (A), wherein the thermoplastic polyurethane resin particles (A) are made of a thermoplastic polyurethane resin obtained by reacting an isocyanate-terminated urethane prepolymer (a1) with an amine (a2), the content of the plasticizer (B) is 5 to 60% by weight based on the weight of the thermoplastic polyurethane resin particles (A), and the content of the fine particles (C) is 0.1 to 10% by weight based on the weight of the thermoplastic polyurethane resin particles (A), and the method for producing a resin particle composition for DTF printing comprises the step of mixing and stirring a mixture (M) containing the amine (a2), an organic solvent (K) having a relative dielectric constant of 5 to 25, and water with the isocyanate-terminated urethane prepolymer (a1) to obtain the thermoplastic polyurethane resin particles (A).

11. A method for producing a resin particle composition for DTF printing according to claim 10, comprising a step of reacting an aliphatic diisocyanate (a1-1), a monool (a1-2), and a diol (a1-3) having a number average molecular weight of 500 to 10,000 to obtain the isocyanate group-terminated urethane prepolymer (a1).

12. A method for producing a resin particle composition for DTF printing according to claim 10 or 11, wherein the equivalent amount of the amine (a2) is 0.70 to 1.00 equivalents per equivalent of the isocyanate group of the isocyanate group-terminated urethane prepolymer (a1).

13. A method for producing a resin particle composition for DTF printing described in claim 10 or 11, wherein the content of the organic solvent (K) is 5 to 30 weight % based on the total weight of the mixture (M) and the isocyanate group-terminated urethane prepolymer (a1).

14. A method for producing a resin particle composition for DTF printing according to claim 10 or 11, comprising the steps of mixing the thermoplastic polyurethane resin particles (A) with the plasticizer (B) and heating the mixture at 40 to 90°C for at least 1 hour to impregnate the thermoplastic polyurethane resin particles (A) with the plasticizer (B).

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