Dye-based printing treatment solution composition, composition set, printing method, and inkjet printing method

Abstract

To provide a printed matter having sufficient color development property, discoloration and fading properties of the printed matter with the passage of time, and fastness such as scratch resistance, which is simply obtained by previously bonding a treatment liquid composition to a fabric containing a fiber having a hydroxyl group, and performing printing on the fabric to which the treatment liquid composition is bonded.SOLUTION: A treatment liquid composition for dye printing is used by bonded to a fabric, and contains a polyester resin having a glass transition temperature of 40°C or higher, a crosslinking agent and water, wherein the fabric contains a fiber having a hydroxyl group.SELECTED DRAWING: None

Description

[Technical Field] 【0001】 The present invention relates to a dye printing treatment solution composition, a composition set, a printing method, and an inkjet printing method. [Background technology] 【0002】 Conventionally, when dyeing fabric with colorants to manufacture printed materials, a technique is known in which the fabric is pre-treated using a treatment solution to improve the color development and fastness of the colorant. As an example of such a technique, Patent Document 1 describes a technique in which a pre-treatment solution consisting of an aqueous composition is applied to polyester fabric. [Prior art documents] [Patent Documents] 【0003】 [Patent Document 1] Japanese Patent Publication No. 2009-249773 [Overview of the project] [Problems that the invention aims to solve] 【0004】 However, Patent Document 1 describes a technique for polyester fabrics and does not describe printing on natural fiber fabrics. Unlike natural fiber fabrics, polyester fabrics can be printed using dyes without the use of a pretreatment solution, and the resulting printed materials usually have good color development and fastness. However, even when the pretreatment solution described in Patent Document 1 is used on natural fiber fabrics, there is a problem in that it is difficult to obtain printed materials that have sufficient color development, fastness, and resistance to color change and fading with this pretreatment solution. [Means for solving the problem] 【0005】 The present invention relates to a treatment liquid composition for use by adhering it to a fabric, comprising a polyester resin having a glass transition temperature of 40°C or higher, a crosslinking agent, and water, wherein the fabric contains fibers having hydroxyl groups, and is a treatment liquid composition for dye printing. [Brief explanation of the drawing] 【0006】 [Figure 1] This flowchart shows an example of the indirect printing recording method of this embodiment. [Modes for carrying out the invention] 【0007】 The following describes in detail an embodiment of the present invention (hereinafter referred to as "this embodiment"), but the present invention is not limited thereto, and various modifications are possible without departing from its essence. 【0008】 1. Dye-based printing treatment solution composition The dye printing treatment liquid composition of this embodiment (hereinafter also referred to as the "treatment liquid composition") is used by applying it to a fabric containing hydroxyl group fibers before dye printing. The treatment liquid composition contains a polyester resin having a glass transition temperature of 40°C or higher, a crosslinking agent, and water. 【0009】 According to this embodiment, by first applying the treatment solution composition to a fabric containing fibers having hydroxyl groups, and then printing a dye onto the fabric to which the treatment solution composition has been applied, it is possible to easily obtain a printed material with sufficient color development, resistance to discoloration and fading over time, and fastness such as abrasion resistance. Although the reason why this embodiment yields such excellent results is not entirely clear, the inventors of the present invention surmise the following. In other words, inks containing disperse dyes, etc., typically used in textile printing, have low affinity for fabrics containing hydroxyl groups, such as cotton, making dye printing difficult. On the other hand, inks containing disperse dyes, etc., readily dye polyester resins due to hydrogen bonding with carboxyl groups, π-π interactions with hydrophobic parts such as phenyl groups, and non-covalent bonds such as van der Waals forces within the structure of the polyester resin. Furthermore, since polyester resin has a high affinity for fabrics containing fibers, it can exist on the fabric. Therefore, by using a treatment composition to adhere the polyester resin to the fabric, the dyeability of inks containing disperse dyes, etc., can be imparted to hydroxyl groups, such as cotton. However, if the polyester resin has few hydrophobic parts in its structure, or if crystallization with the fabric has not progressed, the disperse dye is difficult to penetrate the amorphous parts, making it difficult to dye the polyester resin, and the printed material is prone to fading over time. On the other hand, the treatment solution composition of this embodiment contains a polyester resin with a glass transition temperature of 40°C or higher. Therefore, the polyester resin can crystallize on the fabric, and the disperse dye can impart ink to the crystalline parts of the polyester resin. Thus, according to this embodiment, it is possible to impart sufficient color development as well as excellent resistance to fading over time to the printed material. On the other hand, polyester resin merely adheres to the fabric and does not bind to it. Therefore, even if using polyester resin with a glass transition temperature of 40°C or higher makes it possible to obtain sufficient color development and excellent colorfastness, the durability, such as abrasion resistance, will be insufficient. In this regard, the treatment solution composition of this embodiment contains a crosslinking agent, which makes it possible to bind the polyester resin to the fabric. Therefore, it is presumed that according to this embodiment, it is possible to obtain a printed material that has sufficient color development and excellent colorfastness, as well as excellent durability. However, the reasons are not limited to this. 【0010】 Next, we will explain each component contained in the processing solution composition, but the fabric will be discussed later. 【0011】 1.1. Polyester resins with a glass transition temperature of 40°C or higher The processing solution composition contains a polyester resin with a glass transition temperature of 40°C or higher. By including a polyester resin in the processing solution composition, it is possible to obtain a printed material that has sufficient color development and excellent color change / fading properties. The polyester resin is not particularly limited as long as its glass transition temperature is 40°C or higher. In this embodiment, the glass transition temperature of the polyester resin can be measured, for example, by a differential scanning calorimeter (hereinafter also referred to as "DSC"). 【0012】 When the treated liquid composition is applied to a fabric, a print with better color development, resistance to discoloration and fading, and fastness can be obtained. Therefore, the glass transition temperature is preferably 50°C or higher. The lower limit is, for example, 180°C or lower, and may also be 150°C or lower. 【0013】 The polyester resin, for example, has constituent units derived from polycarboxylic acids and constituent units derived from polyhydric alcohols. 【0014】 Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4′-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfisoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, succinic anhydride, and p-hydroxybenzoic acid, as well as salts thereof. Examples of salts include potassium salts, sodium salts, calcium salts, and magnesium salts. 【0015】 Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolethylsulfonate, and potassium dimethylolpropionate. 【0016】 The polyester resin preferably contains a hydroxyl group, a carboxyl group, a sulfonic acid group, and sodium salts thereof. These groups may be contained singly or in combination of two or more in the polyester resin. 【0017】 The sulfonic acid group-containing polyester resin has, for example, structural units derived from a polyvalent carboxylic acid, structural units derived from a polyhydric alcohol, and structural units derived from a sulfonic acid-containing aromatic monomer. Examples of the sulfonic acid-containing aromatic monomer include 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 4-sulfo-1,8-naphthalenedicarboxylic anhydride, and salts thereof. The salts may refer to the above, and sodium salts are preferred. 【0018】 When the polyester resin contains these groups, the polyester resin can react well with a crosslinking agent and has good adhesion to a fabric containing fibers having hydroxyl groups. Therefore, it becomes possible to obtain a printed matter having more sufficient color development properties, color fading and discoloration resistance, and fastness. 【0019】 Since it has more sufficient color development properties and more excellent color fading and discoloration resistance, the polyester resin preferably contains a hydrophobic portion such as an aromatic group in its structure. 【0020】 The polyester resin can be obtained, for example, by appropriately selecting one or more from the above polyvalent carboxylic acids, polyhydric alcohols, and, if necessary, sulfonic acid-containing aromatic monomers, and synthesizing them by a conventional polycondensation reaction. 【0021】 Commercially available polyester resins can also be used. Examples of commercially available products include Pluscoat® Z-221, Z-446, Z-561, Z-565, RZ-570, Z-592, Z-687, Z-690, Z-730, Z-760, RZ-105, RZ-570, and RZ-760 (all trade names, manufactured by Go-o Chemical Industry Co., Ltd.); and Byronal® MD-1200, MD-1500, and MD-2000 (all trade names, manufactured by Toyobo Co., Ltd.). 【0022】 Polyester resin may be used alone or in combination of two or more types. 【0023】 To obtain a printed product with better color development, resistance to discoloration and fastness, the polyester resin content is preferably 0.5 to 12.5% ​​by mass in terms of solid content relative to the total amount of the processing liquid composition. To obtain a printed product with better color development, resistance to discoloration and fastness, as well as even better fastness, the polyester resin content is more preferably 1.5 to 8.0% by mass in terms of solid content relative to the total amount of the processing liquid composition. To obtain a printed product with better color development, resistance to discoloration and fastness, as well as good texture, the polyester resin content is even more preferably 1.0 to 6.0% by mass in terms of solid content relative to the total amount of the processing liquid composition. To obtain a printed product with better color development, resistance to discoloration and fastness, as well as even better texture, the polyester resin content is even more preferably 1.5 to 4.0% by mass in terms of solid content relative to the total amount of the processing liquid composition. 【0024】 1.2. Crosslinking agents The processing solution composition contains a crosslinking agent. By including a crosslinking agent in the processing solution composition, crosslinking properties can be imparted, making it possible to bind the polyester resin, dye, and fabric together. As a result, it is possible to obtain printed materials that have sufficient color development and excellent resistance to color change and fading, while also possessing excellent colorfastness. 【0025】 The crosslinking agent can be appropriately selected from known crosslinking agents, and may be one that initiates the crosslinking reaction at room temperature or one that initiates the crosslinking reaction with heat. Examples of such crosslinking agents include self-crosslinking agents, compounds having multiple functional groups that react with unsaturated carboxylic acid components in their molecule, and metals having polyvalent coordination sites. 【0026】 To obtain printed materials with better color development, resistance to discoloration and fastness, it is preferable that the crosslinking agent contains isocyanate groups and / or oxazoline groups. 【0027】 Examples of crosslinking agents containing isocyanate groups include water-dispersible (blocked) polyisocyanates. (Blocked) polyisocyanate refers to polyisocyanate and / or blocked polyisocyanate. 【0028】 Examples of water-dispersible polyisocyanates include those obtained by dispersing a polyisocyanate, which has been given hydrophilicity by polyethylene oxide chains, in water with an anionic or nonionic dispersant. 【0029】 Examples of polyisocyanates include diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate; and derivatives (modified products) of these diisocyanates, such as trimethylolpropane adducts, biuret compounds, and isocyanurates. These polyisocyanates may be used individually or in combination of two or more. 【0030】 Water-dispersible blocked polyisocyanates are obtained by blocking the isocyanate groups of water-dispersible polyisocyanates with a blocking agent. Examples of blocking agents include diethyl malonate, ethyl acetoacetate, ε-caprolactam, butanone oxime, cyclohexanone oxime, 1,2,4-triazole, dimethyl-1,2,4-triazole, 3,5-dimethylpyrazole, and imidazole. These blocking agents may be used individually or in combination of two or more. 【0031】 Commercially available crosslinking agents containing isocyanate groups can also be used. Examples of commercially available products include Fixer #100ECO, #104EA, #220, 70ECO, #70, #410, and #400 (all trade names, Murayama Chemical Research Institute Co., Ltd.); and Elastron® BN-11, BN-27, BN-69, and BN-77 (all trade names, Daiichi Kogyo Seiyaku Co., Ltd.). 【0032】 Examples of crosslinking agents containing oxazoline groups include compounds having two or more oxazoline groups in their molecule. Examples of such oxazoline group-containing compounds include 2,2'-bis(2-oxazoline), 2,2'-methylene-bis(2-oxazoline), 2,2'-ethylene-bis(2-oxazoline), 2,2'-trimethylene-bis(2-oxazoline), 2,2'-tetramethylene-bis(2-oxazoline), 2,2'-hexamethylene-bis(2-oxazoline), and 2,2'-octamethylene-bis(2-oxazoline). Examples include 2,2'-ethylene-bis(4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(4,4'-dimethyl-2-oxazoline), bis(2-oxazolinylcyclohexane) sulfide, bis(2-oxazolinylnorbornane) sulfide, and oxazoline ring-containing polymers. These oxazoline group-containing compounds may be used individually or in combination of two or more. 【0033】 Since it becomes possible to more firmly bond the polyester resin, dye, and fabric, and to obtain a printed product with superior durability, a water-soluble oxazoline group-containing compound is preferred as the oxazoline group-containing compound. 【0034】 Commercially available crosslinking agents containing oxazoline groups can also be used. Examples of such commercially available products include Epocross® K-2010, K-2020, K-2030, K-2035E, WS-300, WS-500, and WS-700 (all trade names, manufactured by Nippon Shokubai Co., Ltd.). 【0035】 The crosslinking agent may be used alone or in combination of two or more types. 【0036】 To obtain printed materials with better color development, resistance to discoloration and fading, and fastness, the crosslinking agent content is preferably 0.1 to 10.0% by mass in terms of solid content relative to the total amount of the treatment liquid composition. 【0037】 To obtain printed materials with better color development, resistance to discoloration and fading, and fastness, it is preferable that the mass ratio of polyester resin to crosslinking agent (polyester resin:crosslinking agent) be 1:0.01 to 1:1.2. To obtain printed materials with better color development, resistance to discoloration and fading, and fastness, as well as good texture, it is preferable that the mass ratio of polyester resin to crosslinking agent (polyester resin:crosslinking agent) be 1:0.05 to 1:0.70. Note that if the polyester resin or crosslinking agent is in the form of an emulsion or the like, the mass ratio is calculated on a solid content basis. 【0038】 1.3.Water The processing liquid composition contains water. The water evaporates and dissipates through drying after the treatment solution composition has been applied to the fabric. Examples of suitable water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as ultrapure water from which ionic impurities have been removed as much as possible. Furthermore, water sterilized by ultraviolet irradiation or the addition of hydrogen peroxide is preferable because it can suppress the growth of mold and bacteria when the treatment solution composition is stored for a long period of time. 【0039】 The water content is 30 to 98% by mass, preferably 35 to 96% by mass, and more preferably 40 to 94% by mass, relative to the total amount of the treatment solution composition. By setting the water content within the above range, it is possible to suppress the increase in viscosity of the treatment solution and improve the workability when applying the treatment solution to the fabric, as well as the drying properties after application. For fabrics containing fibers with hydroxyl groups, a water-based treatment solution composition is preferable because it provides higher affinity and greater safety. In this embodiment, "water-based" refers to a composition in which the water content relative to the total amount of the composition is 30% by mass or more. 【0040】 1.4. Other ingredients The treatment solution composition may contain various additives such as surfactants, solubilizers, viscosity modifiers, pH adjusters, antioxidants, preservatives, fungicides, corrosion inhibitors, and chelating agents. Additives may be used individually or in combination of two or more. 【0041】 The additive content is, for example, about 0.01 to 5.0% by mass of the total amount of the treatment liquid composition. 【0042】 1.5. Method for preparing the treatment solution composition The processing liquid composition can be prepared by mixing each component in any order and removing impurities and foreign matter by filtration or other methods as needed. Methods for mixing the components include sequentially adding each component to a container equipped with a stirring device such as a mechanical stirrer or magnetic stirrer, and then stirring and mixing them. Filtration methods include centrifugal filtration and filter filtration. 【0043】 1.6. Physical properties of the treatment solution composition The physical properties of the treatment solution composition can be arbitrarily adjusted depending on the type of fabric and the method of application to the fabric, i.e., the coating method. The coating method for the treatment solution composition will be described later. 【0044】 1.6.1.Viscosity The viscosity of the treatment liquid composition at 20°C is preferably 1.5 to 100 mPa·s. By setting the viscosity of the treatment liquid within the above range, the coating properties, such as the ease with which the treatment liquid spreads when applied to fabric, can be improved. The viscosity of the treatment liquid composition is measured, for example, using a viscoelasticity tester MCR-300 (Pysica). Specifically, it can be measured by adjusting the temperature of the treatment liquid composition to 20°C and reading the shear viscosity (mPa·s) at a shear rate of 200 (1 / s). 【0045】 1.6.2.Surface tension The surface tension of the treatment solution composition at 25°C is preferably 30 to 50 mN / m. By setting the surface tension of the treatment solution composition at 25°C within this range, appropriate wettability and penetration to the fabric are achieved. Furthermore, since the treatment solution composition is more easily absorbed uniformly into the fabric, it is possible to suppress the occurrence of unevenness in the amount of adhesion, i.e., uneven coating, that occurs when applying the treatment solution composition. The surface tension of the treatment solution composition can be measured, for example, using an automatic surface tension meter CBVP-Z (Kyowa Interface Science Co., Ltd.). Specifically, it can be measured by reading the surface tension when a platinum plate is wetted with the treatment solution composition in an environment of 25°C. 【0046】 2. Inkjet ink composition The inkjet ink composition (hereinafter also referred to as "ink composition") is used to print on a fabric to which the processing liquid composition of this embodiment has been applied, in order to produce a printed object. Next, the ink composition will be described. The ink composition according to this embodiment comprises a disperse dye and water. 【0047】 2.1. Disperse dye The ink composition contains a disperse dye as a dye because it provides excellent color development to fabrics to which the treatment solution composition is applied. Disperse dyes are usually particulate colorants that are dispersed in a dispersion medium by a dispersant. Disperse dyes are also usually nonionic dyes that have hydrophilic groups and moderately polar groups. Disperse dyes may be used alone or in combination of two or more types. 【0048】 Examples of disperse dyes include CI Disperse Yellow, CI Disperse Red, CI Disperse Blue, CI Disperse Orange, CI Disperse Violet, CI Disperse Green, CI Disperse Brown, and CI Disperse Black. 【0049】 Among these, sublimation dyes are preferred as dispersants. Here, "sublimation dyes" refer to dyes that have the property of sublimating when heated. Specifically, such sublimation dyes include CI Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, and 86; CI Disperse Orange 1, 1:1, 5, 20, 25, 25:1, 33, 56, and 76; CI Disperse Brown 2; CI Disperse Red 11, 50, 53, 55, 55:1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190:1, and 20 Examples include 7, 239, and 240; CI Bat Red 41; CI Disperse Violet 8, 17, 23, 27, 28, 29, 36, and 57; CI Disperse Blue 14, 19, 26, 26:1, 35, 55, 56, 58, 64, 64:1, 72, 72:1, 81, 81:1, 91, 95, 108, 131, 141, 145, and 359; CI Solvent Blue 36, 63, 105, and 111, etc. 【0050】 In this embodiment, cyan dyes, red dyes, and yellow dyes are preferred because they provide better dyeability and produce prints with sufficient color development on the fabric to which the treatment solution composition is applied. Furthermore, CI Disperse Blue 359 is more preferred as the cyan dye, CI Disperse Red 60 is more preferred as the red dye, and CI Disperse Yellow 54 is more preferred as the yellow dye, as these provide even better dyeability and produce prints with sufficient color development. 【0051】 From the viewpoint of achieving the effects of this embodiment more effectively and reliably, the colorant content is preferably 0.05 to 20% by mass relative to the total amount of the ink composition. 【0052】 2.2.Water The ink composition contains water. The water can refer to the water contained in the above-described treatment liquid composition, including preferred embodiments. 【0053】 From the viewpoint of achieving the effects of this embodiment more effectively and reliably, the water content is preferably 30 to 80% by mass relative to the total amount of the ink composition. 【0054】 2.3. Dispersant The ink composition may contain a dispersant. When an ink composition contains a dispersant, it exhibits excellent dispersibility of disperse dyes and superior clogging resistance. Examples of dispersants include sodium naphthalene sulfonate-formaldehyde condensate and resins. Sodium naphthalene sulfonate-formaldehyde condensate is a compound obtained by formalin condensation of a sulfonate having a naphthalene ring in its molecule, or a salt thereof. Dispersants may be used alone or in combination of two or more. 【0055】 Because they have better dispersibility, it is preferable that the dispersant contains a resin. Examples of resins include urethane resins, styrene-acrylic resins, acrylic resins, fluorene resins, polyolefin resins, rosin-modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and ethylene vinyl acetate resins. Among these, urethane resins and styrene-acrylic resins are preferred, and styrene-acrylic resins are more preferred, due to their excellent resistance to clogging. 【0056】 The urethane resin is not particularly limited as long as it has urethane bonds in its molecule. Examples of urethane resins include polyether-type urethane resins containing ether bonds in the main chain in addition to urethane bonds, polyester-type urethane resins containing ester bonds in the main chain, and polycarbonate-type urethane resins containing carbonate bonds in the main chain. The urethane resin may be used alone or in combination of two or more types. 【0057】 Commercially available urethane resins can also be used. Examples of commercially available products include Takelac® W6110 (product name) from Mitsui Chemicals, Inc., Acrit® WBR-022U (product name) from Taisei Fine Chemical Co., Ltd., Permarin® UX-368T (product name), Euprene® UXA-307 (product name), and U-Coat® UWS-145 (product name) from Sanyo Chemical Industries, Ltd., and Solusbarth® 47000 (product name) from Lubrizol. 【0058】 Examples of styrene-acrylic resins include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene-α-methylstyrene-acrylic acid copolymers, and styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymers. These copolymers may be in any of the following forms: random copolymers, block copolymers, alternating copolymers, and graft copolymers. 【0059】 Commercially available styrene-acrylic resins can also be used. Examples of commercially available products include Joncryl® 67 (trade name) manufactured by BASF Japan Ltd., and Solusbarth® 43000 (trade name) manufactured by Lubrizol. 【0060】 From the viewpoint of achieving the effects of this embodiment more effectively and reliably, the dispersant content is preferably 3.0 to 8.0% by mass relative to the total amount of the ink composition. 【0061】 2.4. Surfactants The ink composition may contain a surfactant. Examples of surfactants include acetylene glycol-based surfactants, fluorine-based surfactants, and silicone-based surfactants. Surfactants may be used individually or in combination of two or more types. 【0062】 Examples of acetylene glycol-based surfactants include 2,4,7,9-tetramethyl-5-decine-4,7-diol and its alkylene oxide adduct, and 2,4-dimethyl-5-decine-4-ol and its alkylene oxide adduct. Commercially available acetylene glycol-based surfactants can also be used. Examples of commercially available products include the Orfin® 104 series (product name) and E series (product name) manufactured by Nisshin Chemical Industry Co., Ltd., and the Surfinol® series (product name) manufactured by Air Products and Chemicals Inc. 【0063】 Examples of fluorinated surfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphate esters, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkylamine oxide compounds. Commercially available fluorine-based surfactants can also be used. Examples of commercially available products include S-144 (product name) and S-145 (product name) manufactured by Asahi Glass Co., Ltd. 【0064】 Examples of silicone-based surfactants include polysiloxane compounds and polyether-modified organosiloxanes. Commercially available silicone-based surfactants can also be used. Examples of commercially available products include BYK® series 306, 307, 333, 341, 345, 346, 347, 348, and 349 (all product names) manufactured by BYK Chemie Japan Co., Ltd. 【0065】 From the viewpoint of achieving the effects of this embodiment more effectively and reliably, the surfactant content is preferably 0.5 to 5.0% by mass relative to the total amount of the ink composition. 【0066】 2.5. Water-soluble organic solvents The ink composition may contain a water-soluble organic solvent. Examples of water-soluble organic solvents include glycerin; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and Examples include glycol monoethers such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and triethylene glycol monomethyl ether; nitrogen-containing solvents such as 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone; and alcohols such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, tert-butanol, iso-butanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol. Water-soluble organic solvents may be used individually or in combination of two or more types. 【0067】 From the viewpoint of achieving the effects of this embodiment more effectively and reliably, the content of the water-soluble organic solvent is preferably 5 to 30% by mass relative to the total amount of the ink composition. 【0068】 2.6. Other ingredients The ink composition may contain various additives, such as solubilizers, viscosity modifiers, pH adjusters, antioxidants, preservatives, fungicides, corrosion inhibitors, and chelating agents for capturing metal ions that may affect dispersion. Additives may be used individually or in combination of two or more. 【0069】 Examples of preservatives include sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, and 1,2-dibenzinthiazolin-3-one. Commercially available preservatives can also be used. Examples of commercially available preservatives include the Proxel® series from Lonza Japan, specifically CRL, BND, GXL, XL-2, and TN (all are trade names). Preservatives may be used individually or in combination of two or more types. 【0070】 The additive content is approximately 0.01 to 5.0% by mass of the total amount of the ink composition. 【0071】 2.7. Method for producing ink compositions Ink compositions can be prepared by mixing disperse dyes, water, and other components as needed, in any order, and removing impurities and foreign matter by filtration or other methods as necessary. Methods for mixing the components include sequentially adding each component to a container equipped with a stirring device such as a mechanical stirrer or magnetic stirrer, and then stirring and mixing them. Filtration methods include centrifugal filtration and filter filtration. 【0072】 Furthermore, in order to better disperse the disperse dye in the ink composition, a dye dispersant may be prepared in advance, and the ink composition may be prepared using the dye dispersant instead of the disperse dye. The dye dispersant can be obtained, for example, by mixing the disperse dye, water, and dispersant in any order and dispersing them using a paint shaker or the like. 【0073】 3. Composition Set The composition set comprises the above-mentioned processing liquid composition and the above-mentioned ink composition. 【0074】 In this embodiment, the treatment solution composition is first applied to a fabric containing fibers having hydroxyl groups to obtain a fabric to which the treatment solution composition is applied. Then, by printing the fabric to which the treatment solution composition is applied with an ink composition, a printed material with sufficient color development, resistance to discoloration and fading over time, and fastness such as abrasion resistance can be easily obtained. 【0075】 4.Fabric The fabric according to this embodiment contains fibers having hydroxyl groups. Examples of fibers containing hydroxyl groups include natural fibers such as cotton, linen, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane that have hydroxyl groups in their structure; and biodegradable fibers such as polylactic acid. Furthermore, the fibers containing hydroxyl groups may also be blends of these fibers. Cotton is preferred as the fabric because it allows for the simple production of printed materials that have sufficient color development, resistance to discoloration and fading, good texture, and reduced yellowing. 【0076】 Examples of fabric forms include woven fabrics, knitted fabrics, nonwoven fabrics, cloths, and clothing and other fashion accessories. Clothing and other fashion accessories include sewn T-shirts, handkerchiefs, scarves, towels, tote bags, cloth bags, curtains, sheets, bedspreads, and furniture such as wallpaper; and fabrics before and after cutting as parts before sewing. These forms include long rolls, cut to predetermined sizes, and product shapes. The fabric only needs to have the treatment liquid composition attached to it, and fabrics that have been pre-treated with the treatment liquid composition may also be used. 【0077】 The fabric weight is preferably, for example, 1.0 to 10.0 oz. Good recording can be achieved when the fabric weight is within this range. 【0078】 As for the fabric, any fabric that contains hydroxyl group fibers may be used, even if it has been pre-colored with dye. The treatment solution composition can suppress the occurrence of treatment marks while ensuring the color development, resistance to discoloration and fastness of the fabric. Therefore, even if the fabric is pre-colored, it can be used as long as it contains hydroxyl group fibers. In other words, even if the fabric is colored, it is possible to print with good color development, maintain resistance to discoloration and fastness, and suppress the occurrence of treatment marks, thereby improving the quality and commercial value of the printed product compared to conventional methods. 【0079】 Examples of dyes used to pre-color fabrics include water-soluble dyes such as acid dyes and basic dyes; disperse dyes used in combination with dispersants; reactive dyes; and solvent dyes. When using cotton fabric, it is preferable to use disperse dyes and reactive dyes suitable for dyeing cotton, with disperse dyes being more preferable. 【0080】 5. Printing Method The printing method of this embodiment includes a step of applying a treatment solution composition to a fabric containing fibers having hydroxyl groups. By going through this step, a fabric to which the treatment solution composition has been applied is obtained. Furthermore, by applying an ink composition to this fabric, a printed product with sufficient color development, resistance to discoloration and fading, and fastness can be obtained. 【0081】 The printing method preferably includes an ink composition application step, in which an ink composition is applied to the fabric to which the processing liquid composition has been applied, following the processing liquid composition application step described above. The ink composition to be applied to the fabric is not particularly limited as long as it contains a disperse dye, and for example, the inkjet ink composition according to this embodiment can be used. Furthermore, the ink composition application step can be described later in the printing method using an inkjet method. The printing method can be applied to various fabrics and can produce good print quality. 【0082】 The amount of treatment solution composition adhering to the fabric is, for example, 0.02 to 0.5 g / cm³. 2 It is preferable to apply it in such a manner that the concentration is 0.02 to 0.3 g / cm³.2 It is more preferable to adhere the treatment solution composition in such a manner. By setting the amount of treatment solution composition to the above range, the treatment solution composition can be adhered more uniformly to the fabric, further suppressing uneven aggregation of the image in the printed material and improving color development. 【0083】 Methods for applying the treatment liquid composition to a fabric include, for example, an immersion coating method in which the fabric is immersed in the treatment liquid composition; a roller coating method in which the treatment liquid composition is applied using a mangle roller and a roll coater; a spray coating method in which the treatment liquid composition is sprayed using a spray device; and an inkjet coating method in which the treatment liquid composition is sprayed using an inkjet method. These coating methods may be used individually to apply the treatment liquid composition to the fabric, or two or more methods may be combined to apply the treatment liquid composition to the fabric. In this embodiment, the degree of design freedom for the amount of treatment liquid composition to be applied is increased, problems during application are less likely to occur, and the treatment liquid composition can be uniformly applied to the fabric. Therefore, it is preferable to apply the treatment liquid composition to the fabric using rollers such as mangle rollers and roll coaters. 【0084】 The printing method may include a drying step for the treatment solution composition, in which the treatment solution composition is applied to the fabric and then dried. The drying of the treatment solution composition may be carried out by natural drying, but it is preferable to dry it with heat, as this improves the amount of treatment solution composition that adheres to the fabric and also improves the drying speed. 【0085】 Examples of heating methods include the heat press method, the atmospheric pressure steam method, the high-pressure steam method, and the thermofix method. Examples of heat sources include infrared rays (lamps). Furthermore, the heating temperature is preferably 180°C or lower. This suppresses the sublimation of the dye due to heat drying, even if the fabric has been pre-colored with dye, thereby preventing fading of the fabric's color. The lower limit of the heating temperature is 100°C or higher, as long as the water and other media contained in the treatment solution composition evaporate. 【0086】 In the printing method, after applying the treatment solution composition to the fabric, a washing step may be included as needed. By including this step in the printing method, components of the treatment solution composition that are not attached to the fabric can be removed. 【0087】 6. Inkjet Printing Method The inkjet printing method is a method of applying an ink composition to a fabric to which a processing liquid composition has been applied, using an inkjet method. By employing the inkjet method, even fine patterns can be easily and reliably formed. Furthermore, it can be applied to various fabrics and produce good print quality. The inkjet printing method also allows for good print quality with minimal color difference between the front and back sides, even on thick fabrics. Examples of inkjet printing methods include the indirect printing method and the direct printing method. 【0088】 6.1. Inkjet Recording Device The inkjet recording device used in the textile printing method is not particularly limited as long as it has at least an ink container for containing an ink composition and a recording head connected thereto, and can eject the ink composition from the recording head to form an image on the fabric to which the processing liquid composition is attached, or on the transfer paper which is an intermediate transfer medium. In addition, either serial or line type inkjet recording devices can be used. These types of inkjet recording devices are equipped with a recording head, and while changing the relative positional relationship between the fabric or transfer paper and the recording head, droplets of the ink composition are ejected from the nozzle holes of the recording head intermittently and in a predetermined volume at predetermined timings. This makes it possible to attach the ink composition to the fabric or transfer paper and form a predetermined transfer image. 【0089】 In general, in serial inkjet recording devices, the direction of transport of the recording medium and the direction of the reciprocating motion of the recording head intersect, and the relative positional relationship between the recording medium and the recording head is changed by the combination of the reciprocating motion of the recording head and the transport motion of the recording medium. In this case, generally, multiple nozzle holes are arranged on the recording head, and rows of nozzle holes, i.e., nozzle rows, are formed along the transport direction of the recording medium. In addition, depending on the type and number of ink compositions, multiple nozzle rows may be formed on the recording head. 【0090】 Furthermore, in line-type inkjet recording devices, the recording head does not perform a reciprocating motion; instead, the relative positional relationship between the recording medium and the recording head is changed by the transport of the recording medium. In this case as well, the recording head generally has multiple nozzle holes, and a row of nozzles is formed along a direction intersecting the transport direction of the recording medium. 【0091】 6.2. Indirect Printing Recording Method The inkjet printing method of this embodiment includes a processing liquid composition attachment step of attaching the processing liquid composition to a fabric containing fibers having hydroxyl groups, an ejection step of ejecting the ink composition from a recording head and attaching it to an intermediate transfer medium, and a transfer step of transferring the ink composition attached to the intermediate transfer medium to the fabric to which the processing liquid composition obtained in the processing liquid composition attachment step has been attached. Specifically, in this printing method, an ink composition containing a disperse dye such as a sublimable dye is ejected from a liquid ejection head, which is a recording head, and attached to an intermediate transfer medium. The surface of the intermediate transfer medium to which the ink composition has been attached and the fabric surface to which the processing liquid composition has been attached are heated facing each other, and the disperse dye contained in the ink composition is transferred to the fabric to which the processing liquid composition has been attached. In this embodiment, such a printing method is also called an indirect printing recording method. With this printing method, good printing can be achieved regardless of the form of the fabric. 【0092】 6.2.1. Process for attaching the treatment liquid composition For the process of applying the processing liquid composition, refer to the printing method described above. 【0093】 6.2.2.Discharge process In the ejection process, the heated ink composition is ejected from the liquid spray head and adhered to the intermediate transfer medium. Specifically, a pressure generating means is driven to eject the ink composition filled in the pressure generating chamber of the liquid spray head from the nozzle. 【0094】 As an intermediate transfer medium, for example, paper such as plain paper and a recording medium provided with an ink-receiving layer can be used. The above-mentioned recording medium provided with an ink-receiving layer is referred to as, for example, inkjet-specific paper and coated paper. Among these, paper provided with an ink-receiving layer containing inorganic particles such as silica is more preferable. This makes it possible to obtain an intermediate recording in which bleeding and other issues are suppressed on the recording surface during the drying process of the ink composition applied to the intermediate transfer medium. Furthermore, with such a medium, it is easier to retain the disperse dye on the surface of the recording surface, and the sublimation of the disperse dye can be carried out more efficiently in the subsequent transfer process. 【0095】 In this process, multiple types of ink compositions may be used. This can, for example, broaden the range of colors that can be expressed. One of the multiple ink compositions may be the ink composition of this embodiment, or two or more may be the ink composition of this embodiment. 【0096】 6.2.3. Transfer Process The transfer process involves heating the surface of the intermediate transfer medium to which the ink composition is attached and the fabric surface to which the processing liquid composition is attached, with these surfaces facing each other, thereby transferring the disperse dye contained in the ink composition to the fabric to which the processing liquid composition is attached. As a result, a printed material is obtained, which is the fabric to which the disperse dye has been transferred and the ink composition has been attached. 【0097】 In this process, the intermediate transfer medium to which the ink composition has been applied should be heated while facing the fabric to which the processing liquid composition has been attached. In this process, it is more preferable to heat the intermediate transfer medium and the fabric to which the processing liquid composition has been attached while they are in close contact. This allows, for example, a clearer image to be recorded on the fabric to which the processing liquid composition has been attached, i.e., dyed. 【0098】 Examples of heating methods include steaming with steam, heat pressing with dry heat, thermosol, HT steamer with superheated steam, and HP steamer with pressurized steam. The fabric to which the ink composition has been applied may be heat-treated immediately, or it may be heat-treated after a predetermined time has elapsed. Dry heat is preferred as the heating method because it yields an impression with sufficient color development, resistance to discoloration and fastness. 【0099】 The heating temperature is preferably 160-220°C, and more preferably 190-210°C. A heating temperature within this range reduces the energy required for transfer, resulting in improved productivity of the printed material. Furthermore, it tends to result in superior color development of the printed material. 【0100】 The heating time, depending on the heating temperature, is preferably 30 to 120 seconds, and more preferably 40 to 90 seconds. Heating within this range reduces the energy required for transfer, resulting in improved productivity of the printed material. Furthermore, it tends to result in superior color development of the printed material. 【0101】 The amount of ink composition that adheres to the fabric through transfer is, for example, 1.5 to 6.0 mg / cm² per unit area of ​​the fabric. 2 It is preferable that the amount of ink composition adhered is within the above range, which improves the color development of images formed by printing, and ensures that the ink adhering to the fabric dries properly, thereby reducing the occurrence of blurring of images. 【0102】 6.2.4. Other processes This method may include intermediate processing steps and post-processing steps as needed. 【0103】 An intermediate processing step may include, for example, a step of preheating the fabric to which the processing liquid composition has been applied. Post-processing steps include, for example, the process of cleaning the printed material. 【0104】 6.2. Direct Printing Recording Method The inkjet printing method may include a processing liquid composition application step, in which a processing liquid composition is applied to a fabric containing fibers having hydroxyl groups, and an ink composition application step, in which an ink composition is ejected from a recording head to apply the ink composition to the fabric to which the processing liquid composition obtained in the processing liquid composition application step has been applied. In this embodiment, such a printing method is also referred to as a direct printing recording method. With this printing method, even fine patterns can be easily and reliably formed. Furthermore, since there is no need to use plates such as intermediate transfer media, it has excellent on-demand capabilities and can be suitably used for small-batch production and multi-product production. 【0105】 6.2.1. Process for obtaining a fabric to which the treatment solution composition has been applied. For the process of applying the processing liquid composition, refer to the printing method described above. 【0106】 6.2.2. Ink composition application process In the ink composition application step, the ink composition is applied to the fabric to which the processing liquid composition has been applied. The ink composition application step may also include a step of further applying the ink composition to the area to which the ink composition has been applied. 【0107】 In the ink composition application process, the maximum amount of ink applied to the fabric is 50-200 mg / cm². 2 Preferably, it is 80-150 mg / cm³ 2 This is more preferable. When the maximum amount of adhesion falls within the above range, the color development is better. In addition, the frictional fastness of the image is also excellent, and uneven aggregation tends to be less noticeable. 【0108】 In this process, it is preferable to heat the fabric to which the processing solution composition has been applied when the ink composition is applied. This allows for, for example, recording a clearer image on the fabric to which the processing solution composition has been applied, i.e., dyeing the fabric. 【0109】 Examples of heating methods include the heat press method, atmospheric pressure steam method, high-pressure steam method, and thermofix method. Examples of heat sources include hot air, infrared rays, and microwaves. 【0110】 During heating, it is preferable that the surface temperature of the heated fabric be between 60 and 180°C. A surface temperature within this range reduces damage to the inkjet head and the fabric, and also allows the ink to spread and penetrate the fabric more evenly. The surface temperature can be measured, for example, using a non-contact thermometer (product name "IT2-80," manufactured by Keyence Corporation). 【0111】 The heating time is preferably, for example, between 5 seconds and 5 minutes. By keeping the heating time within this range, it is possible to sufficiently heat the fabric while reducing damage to the inkjet head and the fabric. 【0112】 6.2.3. Other processes This method may include intermediate and post-processing steps as needed. These steps can be referenced from the other steps in the indirect printing recording method described above. [Examples] 【0113】 The present invention will be described more specifically below with reference to examples and comparative examples. The present invention is not limited in any way by the following examples. 【0114】 1. Preparation of dye printing treatment solution composition (Examples 1-15 and Comparative Examples 1-14) Each component was placed in a mixing tank to obtain the composition shown in Tables 1 and 2, mixed and stirred, and then filtered through a 5 μm membrane filter to obtain the respective treatment liquid compositions. Note that the numerical values ​​for the blending amounts of each component in Tables 1 and 2 represent mass percent. "Solid content" for resins and crosslinking agents also represents mass percent. "Tg" for resins represents the glass transition temperature (°C). "Resin solid content" represents the solid content (parts by mass) of the resin in the treatment solution composition. "Crosslinking agent solid content" represents the solid content (parts by mass) of the crosslinking agent in the treatment solution composition, and "Crosslinking agent solid content / resin solid content ratio" represents the mass ratio calculated on a solid content basis for polyester resin and crosslinking agent. 【0115】 Furthermore, the components shown in Tables 1 and 2 are as follows: 〔resin〕 (Styrene acrylic resin) • 6960: Movinyl (registered trademark) 6960 (product name, Japan Coating Resin Co., Ltd.) (Sulfonic acid group-containing polyester resin) • Z-3310: Pluscoat (registered trademark) Z-3310 (product name, Go-O Chemical Industry Co., Ltd.) • Z-880: Pluscoat (registered trademark) Z-880 (product name, Go-O Chemical Industry Co., Ltd.) • Z-592: Pluscoat (registered trademark) Z-592 (product name, Go-O Chemical Industry Co., Ltd.) • Z-687: Pluscoat (registered trademark) Z-687 (product name, Go-o Chemical Industry Co., Ltd.) • RZ-570: Pluscoat (registered trademark) RZ-570 (product name, Go-o Chemical Industry Co., Ltd.) (Carboxyl group-containing polyester resin) • RZ-760: Pluscoat (registered trademark) RZ-760 (product name, Go-o Chemical Industry Co., Ltd.) (Polyester resin) • MD-1480: Byronal (registered trademark) MD-1480 (product name, Toyobo Co., Ltd.) • MD-2000: Byronal (registered trademark) MD-2000 (product name, Toyobo Co., Ltd.) 【0116】 [Crosslinking agent] • #220: Fixer #220 (product name, Murayama Chemical Research Institute Co., Ltd.) • K-2035E: Epocross (registered trademark) K-2035E (product name, Nippon Shokubai Co., Ltd.) 【0117】 [Table 1] 【0118】 [Table 2] 【0119】 In Comparative Examples 1 and 2, no treatment solution composition was prepared. 【0120】 2. Preparation of inkjet ink composition (Dye dispersants 1-3) Each component was placed in a mixing tank to obtain the compositions shown in Table 3, and dispersed using 0.3 mm zirconia beads in a paint shaker to obtain dye dispersants 1 to 3. The values ​​for each component in Table 3 represent mass percent. 【0121】 Furthermore, the components shown in Table 3 are as follows: [Disperse dye] • Disperse Blue 359: CI Disperse Blue 359 (commercial product) • Disperse Red 60: CI Disperse Red 60 (commercially available product) • Disperse Yellow 54: CI Disperse Yellow 54 (commercial product) 【0122】 [Dispersant] • Solusbarth(R) 43000: Solusbarth(registered trademark) 43000 (product name, acrylic-styrene resin, manufactured by Lubrizol) 【0123】 [Table 3] 【0124】 (C ink, M ink, and Y ink) Each component was placed in a mixing tank to achieve the composition shown in Table 4, and the mixture was stirred with a stirrer for 2 hours. The mixture was then filtered through a 1 μm pore size membrane filter to obtain ink compositions C ink, M ink, and Y ink, respectively. The values ​​for each component in Table 4 represent mass percent. 【0125】 Furthermore, the components shown in Table 4 are as follows: 【0126】 [Dye dispersant] Each of the dye dispersants 1 to 3 obtained above was used. 【0127】 [Surfactants] • BYK(R)-348: BYK(registered trademark)-348 (product name, silicone-based surfactant, manufactured by BYK Chemie Japan Co., Ltd.) 【0128】 [Water-soluble organic solvents] Glycerin Propylene glycol 【0129】 [Preservatives] • Proxel(R) XL-2: Proxel(registered trademark) XL-2 (product name, manufactured by Lonza Japan Co., Ltd.) 【0130】 [Table 4] 【0131】 3. Preparation of the printed material 3.1. Preparation of fabric to which the treatment solution composition is attached. (Examples 1-15 and Comparative Examples 3-12) The treatment liquid compositions of Examples 1 to 15 and Comparative Examples 3 to 12 were used to adhere the treatment liquid compositions to fabrics. Specifically, fabrics to which the treatment liquid compositions had adhered were obtained as follows. As a fabric sample, white cotton braid #4000 (product name, manufactured by Toyobo Co., Ltd.) was immersed in the treatment solution composition, and the treatment solution composition was applied to the fabric using a mangle roller to achieve a wringing ratio of 80%. After drying at 120°C for 2 minutes, it was further dried at 170°C for 1 minute to obtain fabric samples coated with the treatment solution composition. 【0132】 The aperture ratio (S) was calculated using the following formula (1). S(%)=[(AB) / B]×100...(1) In formula (1), S represents the wringing ratio (%), A represents the mass of the fabric to which the treatment liquid composition is applied, and B represents the mass of the fabric before the treatment liquid composition is applied. 【0133】 (Examples 16-20, and Comparative Examples 13 and 14) The treatment liquid compositions of Examples 7, 15, 9, 11, 12, and Comparative Examples 13 and 14 were used to adhere the treatment liquid compositions to the fabric. Specifically, the fabric to which the treatment liquid composition was adhered was obtained as follows. As a fabric sample, the treatment solution composition was uniformly applied to one side of the chest area of ​​a commercially available T-shirt using a spray, covering an area the size of A4 paper. Afterward, it was dried at 120°C for 2 minutes, and then further dried at 170°C for 30 seconds to obtain fabric samples coated with the treatment solution composition. 【0134】 3.2. Preparation of an intermediate recording medium to which the ink composition is attached. (Examples 1-20 and Comparative Examples 1-14) C ink, M ink, and Y ink were respectively filled into cartridges of an inkjet printer PX-G930 (product name, manufactured by Seiko Epson Corporation). Then, on a surface of coated paper (TRANSJET Sportline 1254 (product name), manufactured by Chem Paper) with a coated layer, an ink injection rate of 12 mg / inch was applied at a resolution of 720 dpi x 720 dpi and an ink ejection rate of 100% duty cycle. 2Under the conditions of , each of the three inks was adhered alone so that they did not overlap, and an image having three filling patterns was formed. As a result, an intermediate recording medium to which the ink composition was adhered was obtained. 【0135】 3.3. Dyeing (Examples 1 to 15 and Comparative Examples 3 to 12) The surface on which the image of the intermediate recording medium to which the ink composition obtained above was adhered was formed was heat-transferred to each of the fabrics (cotton blades) to which the treatment liquid composition obtained above was adhered, using a heat press machine TP-608M (trade name, manufactured by Taiyo Seiki Co., Ltd.) at a temperature of 200 °C, a pressure of 4.2 N / cm 3 , and for 60 seconds, respectively obtaining printed fabrics that are fabrics to which C ink, M ink, and Y ink are adhered. 【0136】 (Examples 16 to 20 and Comparative Examples 13 and 14) The surface on which the image of the intermediate recording medium to which the ink composition obtained above was adhered was formed was heat-transferred to each of the fabrics (T-shirts) to which the treatment liquid composition obtained above was adhered, using a heat press machine TP-608M (trade name, manufactured by Taiyo Seiki Co., Ltd.) at a temperature of 200 °C, a pressure of 4.2 N / cm 3 , and for 60 seconds, respectively obtaining printed fabrics that are fabrics to which C ink, M ink, and Y ink are adhered. 【0137】 (Comparative Example 1) The surface on which the image of the intermediate recording medium to which the ink composition obtained above was adhered was formed was heat-transferred to a white polyester fabric Carl Dry K-1 (trade name, Toray Industries, Inc.) using a heat press machine TP-608M (trade name, manufactured by Taiyo Seiki Co., Ltd.) at a temperature of 200 °C, a pressure of 4.2 N / cm 3 , and for 60 seconds, respectively obtaining printed fabrics that are fabrics to which C ink, M ink, and Y ink are adhered. 【0138】 (Comparative Example 2) The surface of the intermediate recording medium to which the ink composition obtained above was attached, and to which the image was formed, was pressed onto a white cotton blade #4000 (product name, Nisshinbo Holdings Inc.) using a heat press machine TP-608M (product name, Taiyo Seiki Co., Ltd.) at a temperature of 200°C and a pressure of 4.2 N / cm². 3 The fabrics were then heat-transferred under the conditions of C ink, M ink, and Y ink, respectively, to obtain printed materials. 【0139】 4. Evaluation Method 4.1. Discoloration Using a fluorescence spectrometer FD-7 (product name, manufactured by Konica Minolta, Inc.), the color intensity (OD value) of printed materials coated with C ink, M ink, and Y ink immediately after printing was measured under the following measurement conditions and at a room temperature of 25°C. Subsequently, each printed material was left at a room temperature of 25°C for 3 days, and the color intensity (OD value) of the printed materials after the period of time was measured under the same conditions. (Measurement conditions) • Observation light source: D65 • Observation field of view: 2° • Status: T • UV filter: Installed 【0140】 The OD values ​​of the printed materials immediately after printing and the OD values ​​of the printed materials after being left for 3 days were compared, and the discoloration and fading properties of each printed material in Examples 1 to 15 and Comparative Examples 1 to 12 were evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6. (Evaluation Criteria) A: The decrease in OD values ​​for all three colors was less than 2%. B: Of the three colors, the decrease in OD value of one of the colors was between 2% and 5%. The decrease in OD value of the other colors was less than 2%. C: Of the three colors, the decrease in OD value of at least one color was 5% or more. The decrease in OD value of the other colors was less than 5%. 【0141】 4.2. Color development 4.2.1. Color development for C ink Each of the printed materials coated with C ink, M ink, and Y ink was left at room temperature (25°C) for 3 days. Subsequently, the color density (OD value) for C ink in each of the printed materials after 3 days was measured using a fluorescence spectrometer FD-7 (product name, manufactured by Konica Minolta, Inc.) under the following measurement conditions and at room temperature (25°C). (Measurement conditions) • Observation light source: D65 • Observation field of view: 2° • Status: T • UV filter: Installed 【0142】 Subsequently, the OD values ​​for the printed materials in Examples 1-15 and Comparative Examples 1 and 3-12 were compared with the OD values ​​for the printed material in Comparative Example 2, and the color development for C ink was evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6. (Evaluation Criteria) A: The OD value was 200% or more compared to the OD value for the printed material in Comparative Example 2. B: Compared to the OD value for the printed material in Comparative Example 2, the OD value was 180% or more but less than 200%. C: Compared to the OD value for the printed material in Comparative Example 2, the OD value was 170% or more but less than 180%. D: Compared to the OD value for the printed material in Comparative Example 2, the OD value was 160% or more but less than 170%. E: The OD value was less than 160% compared to the OD value for the printed material in Comparative Example 2. 【0143】 4.2.2. Color development with M ink Using a fluorescence spectrometer FD-7 (product name, manufactured by Konica Minolta, Inc.), the color density (OD value) for M ink in each printed material after being left for 3 days was measured under the same measurement conditions as described above. 【0144】 Subsequently, the OD values ​​for the printed materials in Examples 1-15 and Comparative Examples 1 and 3-12 were compared with the OD values ​​for the printed material in Comparative Example 2, and the color development properties for M ink were evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6. (Evaluation Criteria) A: The OD value was 190% or higher compared to the OD value for the printed material in Comparative Example 2. B: Compared to the OD value for the printed material in Comparative Example 2, the OD value was 180% or more but less than 190%. C: Compared to the OD value for the printed material in Comparative Example 2, the OD value was 170% or more but less than 180%. D: Compared to the OD value for the printed material in Comparative Example 2, the OD value was 160% or more but less than 170%. E: The OD value was less than 160% compared to the OD value for the printed material in Comparative Example 2. 【0145】 4.2.3. Color development with Y ink Using a fluorescence spectrometer FD-7 (product name, manufactured by Konica Minolta, Inc.), the color intensity (OD value) of each printed material with respect to Y ink was measured after being left for 3 days under the same measurement conditions as described above. 【0146】 Subsequently, the OD values ​​for the printed materials in Examples 1-15 and Comparative Examples 1 and 3-12 were compared with the OD values ​​for the printed material in Comparative Example 2, and the color development with Y ink was evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6. (Evaluation Criteria) A: The OD value was 200% or more compared to the OD value for the printed material in Comparative Example 2. B: Compared to the OD value for the printed material in Comparative Example 2, the OD value was 180% or more but less than 200%. C: Compared to the OD value for the printed material in Comparative Example 2, the OD value was 170% or more but less than 180%. D: Compared to the OD value for the printed material in Comparative Example 2, the OD value was 160% or more but less than 170%. E: The OD value was less than 160% compared to the OD value for the printed material in Comparative Example 2. 【0147】 4.3. Robustness Following the preparation of the stamps described above, stamps coated with C ink, M ink, and Y ink were prepared and left at room temperature (25°C) for 1 hour. Subsequently, the recording surface of the stamps was tested using a JSPS-type friction fastness tester AB-301 (product name, manufactured by Tester Sangyo Co., Ltd.) in accordance with the ISO-105 X12 wet test, and the friction fastness was evaluated using a stain grayscale according to the evaluation criteria below. The evaluation results are in the order of AA, A, B, and C, with AA indicating superior fastness. An evaluation result of B or higher indicates superior fastness. These results are shown in Tables 5 and 6. (Evaluation Criteria) AA: The friction fastness of all three colors exceeds level 3. A: Of the three colors, the friction fastness of one of them was grade 3. The friction fastness of the other colors was above grade 3. B: Of the three colors, the friction fastness of one of the colors was between grade 2 and grade 3. The friction fastness of the other colors was above grade 3. C: Of the three colors, the friction fastness of one of them was below level 2. However, the friction fastness of the other colors was above level 2. 【0148】 4.4. Texture Following the above procedure for preparing printed materials, printed materials with C ink, M ink, and Y ink were prepared, and the texture of the obtained printed materials was evaluated by sensory testing. Specifically, five random judges evaluated the obtained printed materials on whether they were "indistinguishable from the original feel of the fabric" or "the printed material is stiff and the original feel of the fabric is impaired." The results of these evaluations, along with the following evaluation criteria, were used to assess the texture. An evaluation result of B or higher indicates excellent texture. A: Four or more judges responded that the fabric had "no inferiority to the original texture of the woven material." B: Three judges responded that the fabric had "no inferiority to the original texture of the cloth." C: One or two judges responded that the fabric had "no inferiority to the original texture of the material." 【0149】 The results are shown in Table 7. The numerical data and other information in Table 7 are presented in the same way as in Tables 1 and 2. 【0150】 [Table 5] 【0151】 [Table 6] 【0152】 [Table 7] 【0153】 As shown in Tables 5 and 6, it was found that by applying the treatment solution composition of this embodiment to a cotton fabric containing hydroxyl group fibers and then printing on the cotton fabric to which the treatment solution composition has been applied, it is possible to easily obtain a printed material with sufficient color development, resistance to discoloration and fading over time, and fastness such as abrasion resistance. Furthermore, as shown in Table 5, it was found that when the mass ratio of polyester resin to crosslinking agent (polyester resin:crosslinking agent) is in the range of 1:0.01 to 1:1.2, printed materials with better color development, resistance to discoloration and fading, and fastness can be obtained. 【0154】 From a comparison of Examples 1, 3, 6, and 8 with Examples 2, 4, 5, 7, and 9-12, it was found that when the polyester resin content is in the range of 1.5 to 8.0% by mass in terms of solid content relative to the total amount of the treatment liquid composition, a printed material with better color development, resistance to discoloration, and even better durability can be obtained. 【0155】 From a comparison of Examples 7, 9, 11, and 15-19 with Examples 12, 20, and Comparative Examples 13 and 14, it was found that when the polyester resin content is in the range of 1.0 to 6.0% by mass in terms of solid content relative to the total amount of the treatment liquid composition, a printed material with better color development, resistance to discoloration and fading, and fastness, as well as good texture, can be obtained. Furthermore, a comparison of Examples 7, 9, 11, and 15-19 with Examples 12 and 20 revealed that when the mass ratio of polyester resin to crosslinking agent (polyester resin:crosslinking agent) is in the range of 1:0.05 to 1:0.70, printed materials with better color development, resistance to discoloration and fading, and fastness, as well as good texture, can be obtained. 【0156】 From a comparison of Examples 7, 9, 16, and 18 with Examples 11, 12, 15, 17, 19, 20, and Comparative Examples 13 and 14, it was found that when the polyester resin content is in the range of 1.5 to 4.0% by mass in terms of solid content relative to the total amount of the treatment liquid composition, an impression can be obtained that has sufficient color development, resistance to discoloration and fading, and fastness, as well as an even better texture.

Claims

[Claim 1] A composition set comprising a dye printing treatment liquid composition and an inkjet ink composition, comprising a treatment liquid composition application step of applying the dye printing treatment liquid composition to a fabric, The ejection step involves ejecting the inkjet ink composition from the composition set from the recording head and adhering it to an intermediate transfer medium. The process includes a transfer step of transferring the inkjet ink composition attached to the intermediate transfer medium to the fabric to which the dye printing processing liquid composition obtained in the processing liquid composition attachment step is attached. An inkjet printing method, The aforementioned dye printing treatment solution composition comprises a polyester resin having a glass transition temperature of 40°C or higher, a crosslinking agent, and water. The polyester resin comprises one or more selected from the group consisting of hydroxyl groups, carboxyl groups, sulfonic acid groups, and sodium salts thereof. The crosslinking agent comprises at least one group selected from the group consisting of isocyanate groups and oxazoline groups. The mass ratio of the polyester resin to the crosslinking agent (polyester resin:crosslinking agent) is 1:0.03 to 1:1.

0. The inkjet ink composition comprises a disperse dye and water. The fabric contains fibers having hydroxyl groups. Inkjet printing method. [Claim 2] The inkjet printing method according to claim 1, wherein the content of the polyester resin is 0.5 to 12.5% ​​by mass in terms of solid content relative to the total amount of the processing liquid composition. [Claim 3] The inkjet printing method according to claim 1 or 2, wherein the mass ratio of the polyester resin to the crosslinking agent (polyester resin:crosslinking agent) is 1:0.05 to 1:0.70.

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