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

Abstract

The present invention provides a dye printing treatment solution composition that reduces pretreatment marks generated during pretreatment using the treatment solution composition, and that produces printed materials with good color development. [Solution] A dye printing treatment liquid composition comprising a resin, a crosslinking agent, an additive, and water, wherein the additive comprises a compound having a polyoxyalkylene structure, and the compound having a polyoxyalkylene structure is one or more selected from polyoxyalkylene-glyceryl ether, polyoxyalkylene-polyglyceryl ether, and polyoxyalkylene block polymer.

Description

[Technical Field]

[0001] The present invention relates to a dye printing treatment solution composition, a composition set, and a printing method. [Background technology]

[0002] A technique is known in which a sublimation transfer ink used for dyeing polyester fabrics is used to pre-treat fabrics other than polyester using a pre-treatment solution. For example, such a technique discloses a primer solution containing sodium carboxymethylcellulose (CMC) or polyvinyl alcohol (PVA) for printing sublimation dispersion ink for polyester fibers onto cotton fabrics (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2003-201687 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] However, the CMC and PVA contained in the primer solution disclosed in Patent Document 1 have low affinity for sublimation dyes, so the color development of the dye does not improve. In addition, when a pretreatment solution is used, components such as surfactants remaining on the fabric move with the pretreatment solution, and these components become localized, resulting in the occurrence of pretreatment marks. [Means for solving the problem]

[0005] One embodiment of the dye printing treatment solution composition according to the present invention is: It contains resin, crosslinking agent, additives, and water. The aforementioned additive includes a compound having a polyoxyalkylene structure. The compound having the polyoxyalkylene structure is one or more selected from polyoxyalkylene-glyceryl ether, polyoxyalkylene-polyglyceryl ether, and polyoxyalkylene block polymer. [Brief explanation of the drawing]

[0006] [Figure 1] Table 1 shows the compositions of processing liquid compositions 1 to 9. [Figure 2] Table 2 shows the compositions of processing liquid compositions 10 to 18. [Figure 3] Table 3 shows the compositions of processing liquid compositions 19 to 27. [Figure 4] Table 4 shows the composition of the inkjet ink composition. [Figure 5] Table 5 shows the evaluation results for Examples 1 to 9. [Figure 6] Table 6 shows the evaluation results for Examples 10-18. [Figure 7] Table 7 shows the evaluation results for Examples 19-24 and Comparative Examples 1-3. [Modes for carrying out the invention]

[0007] Embodiments of the present invention will be described below. The embodiments described below are examples of the present invention. The present invention is not limited in any way to the embodiments described below and includes various modifications that can be implemented without changing the gist of the present invention. Not all of the configurations described below are necessarily essential to the present invention.

[0008] In this specification, "printing" refers to recording / printing ink onto a recording medium, including fabric, and is also called "printing." Furthermore, the recording medium after printing is referred to as a "printed material" or "printed material."

[0009] In this specification, "inkjet printing" means recording (printing) an ink composition onto a recording medium, including fabric, using an inkjet method.

[0010] 1. Treatment Liquid Composition for Dye Napping The treatment liquid composition for dye napping according to an embodiment of the present invention (hereinafter, also referred to as "treatment liquid composition") includes a resin, a crosslinking agent, an additive, and water. The additive includes a compound having a polyoxyalkylene structure, and the compound having a polyoxyalkylene structure is one or more selected from polyoxyalkylene-glyceryl ether, polyoxyalkylene-polyglyceryl ether, and polyoxyalkylene block polymer.

[0011] In the fabric used for dye napping, when the treatment liquid composition was previously adhered to the fabric and dye napping was performed, pretreatment marks sometimes occurred on the fabric. Specifically, yellowing occurred at the edge of the area where the treatment liquid composition adhered.

[0012] The cause of the pretreatment marks is presumed to be potassium ions, sodium ions, etc. contained in surfactants, pastes, fluorescent whitening agents, etc. used in the fabric. Since the fabric used for dye napping is manufactured through processes using components such as surfactants, pastes, and fluorescent whitening agents, those components remain almost uniformly throughout the fabric. When the treatment liquid composition is adhered to the fabric and dried, the treatment liquid composition moves in the fabric as it dries. Along with the movement of the treatment liquid composition, potassium ions and sodium ions on the fabric surface also move. In particular, when pressure is applied by heat pressing in the drying process, steam escapes from the unpressurized part when the moisture evaporates, so the above-mentioned ions move and localize near the unpressurized part. Furthermore, when the fabric is heated, the above-mentioned ions react with carbon dioxide in the air to form carbonates. It is presumed that the localized carbonates appear as pretreatment marks at the edge of the area where the pretreatment liquid adhered.

[0013] The reason why excellent effects are obtained according to this embodiment is not clear, but the inventors of the present invention presume as follows.

[0014] By containing at least one selected from polyoxyalkylene-glyceryl ether, polyoxyalkylene-polyglyceryl ether, and polyoxyalkylene block polymer as an additive in the treatment liquid composition, the viscosity of the treatment liquid composition in the fabric is improved and the moving speed is decreased. Therefore, the movement and localization of potassium ions and sodium ions associated therewith can be reduced. Further, since the compound having a polyoxyalkylene structure contained in the additive shows nonionic properties when dissolved in water, counterions do not generate in the treatment liquid composition. That is, since sodium ions and the like which are the cause of the pretreatment marks do not generate, it is presumed that carbonates due to the treatment liquid composition are hardly generated.

[0015] Further, it is presumed that when the compound having an oxyalkylene structure penetrates into the fabric in a state where the dye is dissolved or dispersed, the fabric is dyed to the inside, and thereby the printed matter shows good color development. However, the reason is not limited to this.

[0016] Hereinafter, the components that can be contained in the treatment liquid composition for dye printing according to the present embodiment will be described in detail.

[0017] 1.1. Resin The treatment liquid composition for dye printing according to the present embodiment contains a resin.

[0018] The content of the resin is preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 4% by mass or more in terms of solid content with respect to the total amount of the treatment liquid composition. Also, the content of the resin is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less in terms of solid content. When the content of the resin is within the above range, the printed matter shows good color development.

[0019] The glass transition temperature (Tg) of the resin is preferably 25°C or higher, more preferably 35°C or higher, and still more preferably 50°C or higher. When the glass transition temperature of the resin is within the above range, fading of the printed matter over time (hereinafter, also referred to as "fading over time") is reduced.

[0020] Furthermore, the glass transition temperature of the resin is preferably 180°C or lower, more preferably 150°C or lower, and even more preferably 100°C or lower.

[0021] The glass transition temperature can be measured using differential scanning calorimetry (DSC) or similar methods.

[0022] Examples of resins include polyester resins, urethane resins, addition polymerization resins, fluororesins, and natural resins. The shape of the resin is not particularly limited, but it is preferably in the form of resin particles. The resin particles are often handled in emulsion form, i.e., resin dispersion, but they may also be supplied in powder form. The resin particles can be used individually or in combination of two or more types.

[0023] The resin is particularly preferably a polyester resin. The inclusion of a polyester resin in the treatment solution composition results in good color development of the printed material and reduced fading over time.

[0024] Examples of polyester resins include resins containing structural units derived from polycarboxylic acids and structural units derived from polyhydric alcohols.

[0025] Examples of polycarboxylic acids contained in polyester resins include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 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 their salts. Examples of salts include potassium salts, sodium salts, calcium salts, and magnesium salts.

[0026] Examples of polyhydric alcohols contained in polyester resins 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.

[0027] The polyester resin preferably contains hydroxyl groups, carboxyl groups, and sulfonic acid groups, as well as their sodium salts. One or more of these groups may be present in the polyester resin.

[0028] Furthermore, it is also preferable that the polyester resin is a sulfonic acid group-containing polyester resin, comprising structural units derived from the above-mentioned polyhydric carboxylic acid, structural units derived from the above-mentioned polyhydric alcohol, and structural units derived from a sulfonic acid group-containing aromatic monomer.

[0029] Examples of sulfonic acid group-containing aromatic monomers include 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 4-sulfo-1,8-naphthalenedicarboxylic acid anhydride, as well as their salts. Sodium salts are preferred as the salts.

[0030] The inclusion of hydroxyl groups, carboxyl groups, and sulfonic acid groups in the polyester resin improves its reaction with the crosslinking agent, thereby enhancing its bonding properties with fabrics, preferably fabrics containing fibers with hydroxyl groups. As a result, it is possible to obtain printed materials that exhibit better color development and texture, and less fading over time.

[0031] Polyester resins may be obtained, for example, by selecting one or more from the above-mentioned polycarboxylic acids, polyhydric alcohols, and optionally sulfonic acid group-containing aromatic monomers, and synthesizing them by conventional polycondensation reactions. Alternatively, commercially available products may be used.

[0032] Examples of commercially available polyester resins include Elitel® KT-0507, KT-8701, KT-9204, KT-8803 (all product names manufactured by Unitika Ltd.), 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 (all product names manufactured by Go-o Chemical Industry Co., Ltd.), and Byronal® MD-1200, MD-1500, MD-2000 (all product names manufactured by Toyobo MC Co., Ltd.).

[0033] 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. Urethane resins may be synthesized by conventional methods or commercially available products may be used. Examples of commercially available urethane resins include Superflex® 460, 460s, 860, E-2000 (product names manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Rezamin® D-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (product names manufactured by Dainichi Seika Kogyo Co., Ltd.), Takelac® W-6061, WS-6021, W-512-A-6 (product names manufactured by Mitsui Chemicals, Inc.), SunCure® 2710 (product name manufactured by Lubrizol), and Permarin® UA-150 (product name manufactured by Sanyo Chemical Industries, Ltd.).

[0034] Examples of addition polymerization resins include homopolymers or copolymers of acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, acrylonitrile, cyanoacrylate, acrylamide, olefin, styrene, silicone, rosin, terpenes, epoxy, vinyl acetate, vinyl chloride, vinyl alcohol, vinyl ether, vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinylimidazole, and vinylidene chloride.

[0035] The resin may be used alone or in combination of two or more types.

[0036] 1.2. Crosslinking Agents The dye printing treatment solution composition according to this embodiment contains a crosslinking agent.

[0037] The inclusion of a crosslinking agent in the processing solution composition imparts crosslinking properties, enabling the bonding of the resin, dye, and fabric. As a result, the printed material exhibits good color development.

[0038] The crosslinking agent is preferably one or more selected from isocyanate compounds and oxazoline compounds, and more preferably an isocyanate compound. By using an isocyanate compound as the crosslinking agent, the hydroxyl groups contained in the additives described later can be crosslinked effectively, resulting in good color development of the printed material and reduced fading over time.

[0039] Examples of isocyanate compounds include water-dispersible polyisocyanates and water-dispersible block polyisocyanates. The isocyanate compound may be used alone or in combination of two or more types.

[0040] 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.

[0041] 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. Polyisocyanates may be used individually or in combination of two or more.

[0042] Water-dispersible blocked polyisocyanates are obtained by adding a blocking agent to the isocyanate group of a water-dispersible polyisocyanate, thereby inactivating the isocyanate group at room temperature. Examples of blocking agents include active methylene compounds, oxime compounds, lactam compounds, alcohol compounds, phenol compounds, amine compounds, pyrazole compounds, mercaptan compounds, and imidazole compounds. Specifically, examples include diethyl malonate, ethyl acetoacetate, butanone oxime, cyclohexanone oxime, ε-caprolactam, methanol, ethanol, phenol, cresol, 1,2,4-triazole, pyrazole, 3,5-dimethylpyrazole, and imidazole. Blocking agents may be used alone or in combination of two or more.

[0043] The crosslinking agent is preferably an isocyanate compound having an isocyanurate skeleton. Since an isocyanate compound having an isocyanurate skeleton has at least three crosslinking points, the bonding between the resin and the fabric can be more favorably improved. As a result, a printed product with excellent color development can be obtained.

[0044] Examples of commercially available isocyanate compounds include Fixer #220, #70, #70ECO, #400, #410, #100ECO, #104EA, and #200ECO (all product names manufactured by Murayama Chemical Research Institute Co., Ltd.), and Elastron® BN-11, BN-27, BN-77, and BN-69 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[0045] As oxazoline compounds, compounds having two or more oxazoline groups in the molecule are preferred. Examples of oxazoline compounds containing two or more oxazoline groups in the molecule include 2,2'-bis(2-oxazoline), 2,2'-methylene-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- Examples include oxazolines, 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. The oxazoline compounds may be used individually or in combination of two or more.

[0046] Oxazoline compounds may be synthesized using conventional methods, or commercially available compounds may be used.

[0047] Examples of commercially available oxazoline compounds include Epocross® WS-300, WS-500, WS-700, K-2010E, K-2020E, and K-2035E (all manufactured by Nippon Shokubai Co., Ltd.).

[0048] The crosslinking agent may be used alone or in combination of two or more types.

[0049] The crosslinking agent content is preferably 0.5% to 5% by mass, more preferably 1% to 3% by mass, and even more preferably 1% to 2.5% by mass, based on the solid content relative to the total amount of the processing liquid composition. When the crosslinking agent content is within the above range, a printed material with good color development can be obtained.

[0050] 1.3. Additives The dye printing treatment solution composition according to this embodiment includes an additive. The additive includes a compound having a polyoxyalkylene structure, and the compound having a polyoxyalkylene structure is one or more selected from polyoxyalkylene-glyceryl ether, polyoxyalkylene-polyglyceryl ether, and polyoxyalkylene block polymer.

[0051] The inclusion of additives in the treatment solution composition improves its viscosity, reducing the movement speed of the treatment solution composition within the fabric during the drying process. As a result, the movement and localization of sodium ions and other elements on the fabric due to the movement of the treatment solution composition are reduced, thereby reducing the occurrence of pre-treatment marks.

[0052] Furthermore, the polyoxyalkylene compounds contained in the additive exhibit nonionic properties when dissolved in water, thus preventing the generation of counterions in the treatment solution composition. In other words, sodium ions and other substances that cause pretreatment residue are not generated, thus preventing pretreatment residue caused by the treatment solution composition containing the additive.

[0053] Furthermore, the additive penetrates the fabric in a state where the dye is dissolved or dispersed, allowing the fabric to be dyed all the way through. Because the dissolved or dispersed state of the dye can be maintained, some of the additive remaining on the dried fabric after the treatment solution composition has been applied to the fabric can temporarily hold the diffused dye when the image formed by the dye is heat-transferred to the fabric. As a result, the resin can be dyed well, and a print with good color development can be obtained.

[0054] Compounds having a polyoxyalkylene structure, such as polyoxyalkylene-glyceryl ether, polyoxyalkylene-polyglyceryl ether, and polyoxyalkylene block polymers, have hydroxyl groups in their molecules. The hydroxyl groups of the additive bind to the bonds formed by the crosslinking agent, and the introduction of a flexible polyoxyalkylene structure between the bonds of the crosslinking agent extends the bonds and reduces the deterioration of texture associated with crosslinking.

[0055] The compound having the polyoxyalkylene structure described above preferably has two or more hydroxyl groups, and more preferably three or more. Having more than the above-mentioned number of hydroxyl groups in the compound having the polyoxyalkylene structure extends the bond formed by the crosslinking agent, and the crosslinking... This reduces the deterioration of the fabric's texture. Furthermore, hydroxyl groups bond between the bonds created by the crosslinking agent, forming part of a three-dimensional crosslinked structure, which strengthens the bond between the resin, dye, and fabric, resulting in better color development.

[0056] The number of carbon atoms in the oxyalkylene group constituting the polyoxyalkylene structure is preferably 2 or more, more preferably 3 or more. Furthermore, the number of carbon atoms in the oxyalkylene group is preferably 4 or less. Examples of such polyoxyalkylene structures include polyoxyethylene structures, polyoxypropylene structures, and polybutylene structures.

[0057] Compounds having a polyoxyalkylene structure may have oxyalkylene groups with different numbers of carbon atoms in their molecules. Examples of structures having oxyalkylene groups with different numbers of carbon atoms include a mixed structure of polyoxyethylene and polyoxypropylene, and a mixed structure of polyoxybutylene, polyoxyethylene, and polyoxypropylene.

[0058] Compounds having a polyoxyalkylene structure adopt a structure in which oxyalkylene groups with different numbers of carbon atoms are present in the molecule. As a result, some of the alkylene groups in the molecule act as hydrophobic groups, and the compound exhibits amphiphilicity. This improves the affinity between hydrophobic dyes and hydrophilic fabric fibers, allowing dyeing to penetrate deep into the fabric, resulting in better color development and reduced fading over time.

[0059] Examples of commercially available compounds having a polyoxyalkylene structure include Sannix® GP-250, GP-400, GP-600, GP-1000, Newport® PE-34, PE-61, PE-62, PE-71 (all product names manufactured by Sanyo Chemical Industries, Ltd.), Uniox® G-450, G-750, Uniol® TG-330, TG-1000R, WILBRIDE® S-753 (all product names manufactured by NOF Corporation), SC-P750, SC-P1000, SC-P1600, SC-E350, SC-E750, SC-E1000, SC-E1500 (all product names manufactured by Sakamoto Pharmaceutical Co., Ltd.).

[0060] The number-average molecular weight (Mn) of the compound having a polyoxyalkylene structure is preferably 150 or more, more preferably 200 or more, and even more preferably 250 or more. When the molecular weight is within the above range, the viscosity of the treatment liquid composition can be improved and the occurrence of pretreatment residue can be reduced. Furthermore, the number-average molecular weight of the compound having a polyoxyalkylene structure is preferably 2500 or less, more preferably 2000 or less, and even more preferably 1000 or less. In the case where there are multiple types of compounds having a polyoxyalkylene structure, the number-average molecular weight (Mn) can be a weighted average, which is the sum of the products of the number-average molecular weight of each compound having a polyoxyalkylene structure and the content of each compound in the additive.

[0061] The additive content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to the total amount of the treatment liquid composition. When the additive content is within the above range, the occurrence of pretreatment marks is reduced and the color development is also good. Furthermore, the additive content is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, relative to the total amount of the treatment liquid composition.

[0062] 1.4. Organic Solvents The treatment solution composition according to this embodiment may contain an organic solvent.

[0063] The inclusion of an organic solvent allows for good dyeing by dissolving or dispersing the dye in some of the organic solvent remaining on the fabric during the dye transfer process.

[0064] Examples of organic solvents include glycols, glycol monoethers, nitrogen-containing solvents, and alcohols.

[0065] Examples of glycols include 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.

[0066] Examples of glycol monoethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and triethylene glycol monomethyl ether.

[0067] Examples of nitrogen-containing solvents include 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone.

[0068] Examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, tert-butanol, isobutanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol.

[0069] The organic solvent preferably contains glycols, and more preferably contains 1,2-hexanediol.

[0070] The content of the organic solvent is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 15% to 30% by mass, based on the total amount of the treatment liquid composition. When the content of the organic solvent is within the above range, the occurrence of pretreatment marks is reduced and the color development of the printed material can be improved.

[0071] 1.5.Water The processing liquid composition according to this embodiment contains water.

[0072] 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.

[0073] The water content is preferably 30% to 98% by mass, more preferably 40% to 96% by mass, and even more preferably 50% to 94% by mass, relative to the total amount of the treatment liquid composition. When the water content is within the above range, it prevents an excessive increase in the viscosity of the treatment liquid composition and allows it to be adjusted to an appropriate range.

[0074] 1.6. Other ingredients The treatment solution composition according to this embodiment includes surfactants, solubilizers, thickeners, pH adjusters, antioxidants, preservatives, fungicides, and chelating agents (hereinafter also referred to as "other components"). It may include.

[0075] The content of other components is, for example, 0.01% by mass or more and 5.0% by mass or less, relative to the total amount of the treatment liquid composition.

[0076] 1.7. 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 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.

[0077] 1.8. Physical properties of the processing solution composition 1.8.1.Viscosity The viscosity of the processing liquid composition at 20°C is preferably 1.5 mPa·s to 15.0 mPa·s, and more preferably 3.0 mPa·s to 13.0 Pa.

[0078] By setting the viscosity of the treatment solution composition within the above range, the treatment solution composition becomes less likely to move when applied to the fabric and dried, thereby reducing pre-treatment marks. Furthermore, the treatment solution composition tends to remain within the fabric, resulting in good color development and reduced fading over time.

[0079] The viscosity of the treatment liquid composition was measured using a viscoelasticity tester MCR-301 (manufactured by Anton Paar) at 20°C with a shear rate of 10 [s]. -1 ] to 1000[s -1 The viscosity can be measured by increasing the setting and reading the viscosity at a Shear Rate of 200.

[0080] 1.8.2.Surface tension The surface tension of the treatment liquid composition at 25°C is preferably 30 mN / m to 50 mN / m. When the surface tension of the treatment liquid composition at 25°C is within the above range, it exhibits appropriate penetration and wettability to the fabric. Furthermore, since the treatment liquid composition is more easily absorbed uniformly by the fabric, it is possible to suppress the occurrence of differences in the amount of adhesion, i.e., uneven coating, that occurs when applying the treatment liquid composition.

[0081] 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.

[0082] 2. Composition Set A composition set according to one embodiment of the present invention comprises the above-described dye printing treatment liquid composition and an inkjet ink composition (hereinafter also referred to as "ink composition").

[0083] The composition set according to this embodiment is used to obtain a printed object by first applying the processing liquid composition to a fabric, and then printing the fabric with the ink composition onto it. Because the printed object obtained in this way has the processing liquid composition applied to the fabric, pre-treatment marks caused by the processing liquid composition are reduced, and it exhibits excellent color development. Furthermore, the fading of the printed object over time is also reduced.

[0084] The dye printing treatment liquid composition included in the composition set according to this embodiment is as described above. As it has been explained in detail, the explanation will be omitted here. Below, the inkjet ink compositions included in the composition set according to this embodiment will be described.

[0085] 2.1. Inkjet Ink Compositions The inkjet ink composition is used when printing on a fabric to which the above-described processing liquid composition has been applied. In the composition set according to this embodiment, the inkjet ink composition may be one type or a combination of two or more types.

[0086] The ink composition used in this embodiment comprises a disperse dye and water.

[0087] 2.1.1.Disperse dye The inkjet ink composition contains a disperse dye as a dye. The inclusion of a disperse dye in the ink composition allows for good color development when printing on fabric to which the processing solution composition has been applied.

[0088] Disperse dyes are colorants that typically form particulate matter and are dispersed in a dispersion medium by a dispersant. Disperse dyes are usually nonionic dyes that have hydrophilic groups and moderately polar groups.

[0089] 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.

[0090] As a disperse dye, sublimation dyes are preferred. Sublimation dyes are disperse dyes that sublimate when heated.

[0091] Specifically, the 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 207. Examples include 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.

[0092] 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 preferred as the cyan dye, CI Disperse Red 60 as the red dye, and CI Disperse Yellow 54 as the yellow dye, as these provide even better dyeability and produce prints with sufficient color development.

[0093] Disperse dyes may be used individually or in combination of two or more types.

[0094] The content of the disperse dye is preferably 0.05% by mass or more and 20% by mass or less, relative to the total amount of the ink composition.

[0095] 2.1.2.Water The inkjet ink composition contains water. The water may be in a preferred form as well as in the processing liquid. The composition is the same as described in section "1.5. Water".

[0096] The water content is preferably 30% by mass or more and 80% by mass or less, relative to the total amount of the ink composition.

[0097] 2.1.3. Dispersant The inkjet ink composition may contain a dispersant. The inclusion of a dispersant in the ink composition improves the dispersibility of the disperse dye, thereby reducing clogging of the inkjet recording device during printing.

[0098] The dispersant is not particularly limited, but examples 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. The dispersant may be used alone or in combination of two or more.

[0099] The dispersant preferably 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. Urethane resins and styrene-acrylic resins are preferred, and styrene-acrylic resins are more preferred, due to their excellent resistance to clogging.

[0100] The dispersant content is preferably 3.0% by mass or more and 8.0% by mass or less, relative to the total amount of the ink composition. When the dispersant content is within the above range, the disperse dye can be stably dispersed.

[0101] 2.1.4. Surfactants The inkjet ink composition may contain a surfactant. The surfactant is not particularly limited, but examples include acetylene glycol-based surfactants, fluorine-based surfactants, and silicone-based surfactants. The surfactant may be used alone or in combination of two or more.

[0102] 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.

[0103] Commercially available acetylene glycol-based surfactants can also be used. Examples of commercially available products include the Orphin® E series (product name manufactured by Nisshin Chemical Industry Co., Ltd.) and the Surfinol® series (product name manufactured by Air Products & Chemicals).

[0104] Examples of fluorinated surfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphate esters, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkylamine oxide compounds.

[0105] Commercially available fluorine-based surfactants can also be used. An example of a commercially available product is the Surflon® series (a product name manufactured by AGC Seimi Chemical Co., Ltd.).

[0106] Examples of silicone-based surfactants include polysiloxane compounds and polyether-modified organosiloxanes.

[0107] Commercially available silicone-based surfactants can also be used. Examples of commercially available products include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, and BYK-349 (all product names manufactured by BICHEMIE Japan Co., Ltd.).

[0108] The surfactant content is preferably 0.5% by mass or more and 5.0% by mass or less, relative to the total amount of the ink composition.

[0109] 2.1.5. Water-soluble organic solvents The inkjet ink composition may contain a water-soluble organic solvent.

[0110] Examples of water-soluble organic solvents include glycols, glycol ethers, nitrogen-containing solvents, alcohols, and glycerin.

[0111] Examples of glycols include 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.

[0112] Examples of glycol monoethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and triethylene glycol monomethyl ether (methyl triglycol).

[0113] Examples of nitrogen-containing solvents include 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone.

[0114] Examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, tert-butanol, isobutanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol.

[0115] Water-soluble organic solvents may be used individually or in combination of two or more types.

[0116] Among these, glycerin, glycols, and glycol monoethers can primarily function as penetrating agents and / or humectants. Glycol monoethers tend to have strong penetrating properties, while glycerin and glycols tend to have strong humectant properties.

[0117] The content of the water-soluble organic solvent is preferably 5% by mass or more and 30% by mass or less, relative to the total amount of the ink composition.

[0118] 2.1.6. Other Ingredients Inkjet ink composition contains a solubilizer, viscosity modifier, pH adjuster, antioxidant, and anti-inflammatory agent. The ink composition may also contain antifungal agents, fungicides, corrosion inhibitors, and chelating agents for capturing metal ions that affect dispersion (hereinafter also referred to as "other components of the ink composition"). The other components of the ink composition may be used individually or in combination of two or more types.

[0119] Examples of preservatives include sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, and 1,2-dibenzinthiazolin-3-one.

[0120] Commercially available preservatives can also be used. Examples of commercially available preservatives include Proxel® GXL (a product name manufactured by Lonza). Preservatives may be used individually or in combination of two or more types.

[0121] The content of other components in the ink composition is 0.01% by mass or more and 5.0% by mass or less, based on the total amount of the ink composition.

[0122] 2.2 Method for Manufacturing Inkjet Ink Compositions Inkjet ink compositions are obtained by mixing disperse dyes, water, and other components as needed in any order, and removing impurities by filtration or other means as necessary. A preferred method for mixing the components is to sequentially add the materials to a container equipped with a stirring device such as a mechanical stirrer or magnetic stirrer and then stir-fry them. As for filtration methods, centrifugal filtration, filter filtration, etc., can be used as needed.

[0123] Furthermore, in order to better disperse the disperse dye in the ink composition, a dye dispersion may be prepared in advance by mixing the disperse dye, a dispersant, and a portion of the water in any order and dispersing them using a paint shaker or the like. The ink composition can then be prepared using the prepared dye dispersion and the remaining components.

[0124] 3. Printing method 3.1. Process for attaching the treatment liquid composition A printing method according to one embodiment of the present invention includes a process of applying a processing liquid composition to a fabric.

[0125] This process allows for the acquisition of a fabric to which the treatment solution composition has been applied. By applying the inkjet ink composition to this fabric, the ink composition exhibits good color development and reduces fading over time.

[0126] The printing method can be applied to various fabrics and can produce good print quality.

[0127] Examples of fabrics include natural fibers such as cotton, linen, wool, leather, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, acrylic, and polyurethane; and biodegradable fibers such as polylactic acid. Furthermore, the fabric may be a blend of the above fibers.

[0128] In this embodiment, the fabric preferably contains fibers having hydroxyl groups, and more preferably is cotton. The fibers having hydroxyl groups may be blended fibers. By including fibers having hydroxyl groups in the fabric, it is possible to obtain a printed material that exhibits excellent color development while maintaining the texture of the fabric.

[0129] 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, skirts, towels, tote bags, cloth bags, curtains, sheets, bedspreads, and wallpaper. Furniture; examples include fabrics before and after cutting as components before sewing. The forms of fabrics before and after cutting include long rolls, fabrics cut to a predetermined size, and fabrics in the shape of products. 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.

[0130] The weight of the fabric is preferably, for example, between 1.0 oz and 10.0 oz. When the weight of the fabric is within the above range, good printing can be achieved.

[0131] As for the fabric, uncolored white fabric and fabric that has been pre-colored with dye can be used. For white fabric, fluorescent whitening agents may be used to maintain or improve the apparent whiteness. Fluorescent whitening agents used during manufacturing may remain in the fabric, and sodium ions contained in these residual fluorescent whitening agents are thought to cause pre-treatment marks. The processing solution composition used in this embodiment can reduce the occurrence of pre-treatment marks, so even when using fabric that has been treated with fluorescent whitening agents, it is possible to obtain printed materials with fewer pre-treatment marks. Therefore, the printing method according to this embodiment is particularly suitable when the fabric is white cotton and the fabric is in the form of a T-shirt. Furthermore, even with pre-colored fabric, pre-treatment using the processing solution composition used in this embodiment results in printed materials with better color development.

[0132] 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, and reactive dyes are more preferable.

[0133] The amount of the treatment solution composition adhering to the fabric is, for example, 0.02 g / cm³. 2 More than 0.5g / cm 2 It is preferable to apply it so that the following concentration is present: 0.02 g / cm³ 2 More than 0.3g / cm 2It is more preferable to apply the treatment solution composition as follows. When the amount of treatment solution composition applied is within the above range, the treatment solution composition can be applied more uniformly to the fabric, further suppressing uneven aggregation of the image in the printed material and enabling good color development.

[0134] The method for applying the treatment liquid composition to the fabric is not particularly limited as long as the treatment liquid composition can be applied to at least a portion of the fabric. Examples of methods for applying the treatment liquid composition include 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 applied by an inkjet method. The coating method may be used individually or in combination of two or more methods.

[0135] In this embodiment, it is preferable to use a roller coating method, such as applying the coating with a mangle roller or a roll coater. By using a roller coating method, the amount of treatment liquid composition that adheres can be adjusted, and the treatment liquid composition can be uniformly applied to the fabric.

[0136] 3.2.Drying process The printing method according to this embodiment preferably includes a drying step to dry the treatment liquid composition applied to the fabric, following a treatment liquid composition application step in which the treatment liquid composition is applied to the fabric. From the viewpoint of improving the amount of treatment liquid composition applied to the fabric and improving the drying speed, it is preferable to use a drying method that involves heating. The fabric to which the treatment liquid composition has been applied may be preheated before the drying step.

[0137] Heating methods in the drying process include, for example, heat pressing, atmospheric pressure steaming, and high pressure. Examples include the steam method and the thermofix method. Among these, the heat press method, which applies heat and pressure simultaneously, is preferred. By using the heat press method, when water in the processing liquid composition evaporates, the steam escapes from areas where no pressure is applied, so residual components and carbonates in the fabric also move to those areas and tend to become localized. Therefore, the printing method according to this embodiment becomes even more effective. Furthermore, there are no particular limitations on the heat source used for heating, but for example, hot air, infrared lamps, and microwaves can be used.

[0138] The drying temperature is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 180°C or lower. When the drying temperature is within the above range, even if the fabric has been dyed with dye beforehand, the sublimation of the dye due to heat drying can be suppressed, and the fading of the fabric color can be reduced. Furthermore, the drying temperature is preferably 50°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher.

[0139] The heating time during drying is preferably, for example, between 1 second and 5 minutes. When the heating time is within the above range, volatile components such as water and organic solvents can be suitably evaporated from the fabric, and damage to the fabric can be reduced.

[0140] 3.3. Ink composition application process The printing method according to this embodiment 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, after the processing liquid composition application step or drying step. As the ink composition to be applied to the fabric, the above-mentioned inkjet ink composition can be used. Furthermore, the ink composition application step can be performed using an inkjet printing method.

[0141] Inkjet printing is a method of applying an ink composition to a fabric coated with a processing liquid composition using an inkjet method. By using the inkjet method, the amount of ink ejected can be controlled, and fine patterns and images can be formed. Furthermore, inkjet printing can be applied regardless of the weight or type of fabric, and good printing with little color difference between the front and back can be achieved even on thick fabrics. Examples of inkjet printing methods include indirect printing and direct printing.

[0142] In the indirect printing recording method, strictly speaking, what is attached to the fabric is not the ink composition itself, but only some of the components contained in the ink composition, such as the disperse dye. In this specification, the phrase "attaching the ink composition to the fabric" is used to include cases where only some of the components contained in the ink composition are attached.

[0143] 3.3.1. Inkjet Recording Device The inkjet recording device used in the inkjet 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 a fabric to which a processing liquid composition is attached, or on a transfer paper which is an intermediate transfer medium.

[0144] Both serial and line type inkjet recording devices can be used. Both types of inkjet recording devices are equipped with an inkjet head, and by changing the relative positional relationship between the inkjet head and the fabric or intermediate transfer medium, ink droplets are ejected from the nozzle holes of the inkjet head at a predetermined timing and in a predetermined volume, thereby adhering the ink to the fabric or intermediate transfer medium and forming a predetermined image.

[0145] Generally, in serial inkjet recording devices, the transport direction of the recording medium and the inkjet The reciprocating motion of the inkjet head intersects with that of the recording medium, and the combination of the inkjet head's reciprocating motion and the recording medium's transport motion changes the relative positional relationship between the recording medium and the inkjet head. In this case, generally, the inkjet head has multiple nozzle holes, and the nozzle holes are formed along the transport direction of the recording medium. In addition, depending on the type and number of ink compositions, the inkjet head may also have multiple rows of nozzles.

[0146] Furthermore, in line-type inkjet recording devices, the inkjet head does not perform a reciprocating motion; instead, the relative positional relationship between the recording medium and the inkjet head is changed by the transport of the recording medium. In this case as well, the inkjet head generally has multiple nozzle holes, and rows of these nozzle holes are formed along a direction intersecting the transport direction of the recording medium.

[0147] 3.3.2. Indirect Printing Recording Method In the indirect printing recording method, an ink composition containing a disperse dye such as a sublimation dye is ejected by a liquid spray head, which is a recording head, and adhered to an intermediate transfer medium. 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 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 is attached. With this indirect printing recording method, good printing can be achieved regardless of the form of the fabric.

[0148] As the intermediate transfer medium, for example, paper such as plain paper or a recording medium provided with an ink-receiving layer can be used. Recording media provided with an ink-receiving layer are referred to as, for example, inkjet-specific paper or coated paper. As the recording medium provided with an ink-receiving layer, paper provided with an ink-receiving layer containing inorganic particles such as silica is more preferable. By providing an ink-receiving layer containing inorganic particles, an intermediate recording can be obtained 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 a recording medium provided with such an ink-receiving layer, 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.

[0149] In the transfer process, the recording surface to which the ink composition of the intermediate transfer medium is attached and the fabric surface to which the processing liquid composition is attached are heated facing each other, causing the disperse dye contained in the ink composition to sublimate and transfer to the fabric to which the processing liquid composition is attached. As a result, a printed object is obtained in which the disperse dye has been transferred to the fabric to which the processing liquid composition is attached.

[0150] In this process, the intermediate transfer medium to which the ink composition is attached is heated while facing the fabric to which the processing liquid composition is attached, and it is more preferable to heat the intermediate transfer medium and the fabric in close contact. This allows for the recording of a clearer image on the fabric.

[0151] Examples of heating methods include dry heat heat press, atmospheric pressure steam and high-pressure steam, and thermofix. The fabric to which the ink composition is attached may be heated immediately, or it may be heated after a predetermined time has elapsed. Dry heat is preferred for the heating method. Using dry heat tends to result in good color development while maintaining the desired texture of the printed material.

[0152] As a heating method, it is preferable to use a dry heat heat press method. Normally, in dry heat heat press, when heating, the moisture contained in the fabric turns into steam from the unpressurized area. At that time, carbonates such as sodium carbonate and potassium carbonate generated in the fabric move and localize in the unpressurized area, which may appear on the surface of the fabric as pre-treatment marks. The treatment liquid composition in this embodiment contains a compound having a polyoxyalkylene structure, which improves the viscosity of the treatment liquid composition. Therefore, even when using a heat press, the treatment liquid composition does not affect the fabric. Movement within the fabric is reduced, and consequently, the localization of carbonates is also reduced, resulting in a decrease in the occurrence of pretreatment marks.

[0153] The heating temperature is preferably between 160°C and 220°C, and more preferably between 190°C and 210°C. When the heating temperature is within the above range, the energy required for transfer can be reduced, and the productivity of the printed material tends to be better. In addition, the color development of the printed material tends to be better.

[0154] The heating time in the transfer process depends on the heating temperature, but is preferably 30 seconds to 120 seconds, and more preferably 40 seconds to 90 seconds. When the heating time in the transfer process is within the above range, the energy required for transfer can be reduced, and the productivity of the printed material tends to be better. In addition, the color development of the printed material tends to be better.

[0155] The amount of ink composition that adheres to the fabric through transfer is, for example, 1.5 mg / cm² per unit area of ​​the fabric. 2 More than 6.0mg / cm 2 The following is preferable: When the amount of ink composition attached is within the above range, the color development of the image formed by printing is improved, and the occurrence of blurring of the image is reduced as the ink composition attached to the fabric dries suitably.

[0156] 3.3.3. Direct Printing Recording Method In the direct printing and dyeing recording method, an ink composition is ejected from a recording head, and the ink composition is directly adhered to a fabric to which a treatment liquid composition obtained by a treatment liquid composition adhesion step is adhered. In the direct printing and dyeing recording method, since an intermediate transfer medium is not used, it has excellent on-demand properties and can cope with multi-variety and small-lot production.

[0157] In the direct printing and dyeing recording method, the ink composition may be further adhered onto an area where the ink composition has already been adhered.

[0158] In the direct printing and dyeing recording method, the maximum adhesion amount to the fabric is preferably 50 mg / cm 2 or more and 200 mg / cm 2 or less, and more preferably 80 mg / cm 2 or more and 150 mg / cm 2 or less. When the maximum adhesion amount is within the above range, good color development is shown. Also, the aggregation unevenness of the image in the printed matter tends to be reduced.

[0159] In this step, when adhering the ink composition to the fabric to which the treatment liquid composition is adhered, it is preferable to heat. By heating when adhering the ink composition, a clearer image can be recorded on the fabric.

[0160] Examples of the heating method include a heat press method, an atmospheric pressure steam method, a high pressure steam method, and a thermofix method. Also, the heat source for heating is not particularly limited, and for example, warm air, an infrared lamp, and microwaves can be used.

[0161] The surface temperature of the fabric during heating is preferably 60°C or more and 180°C or less. When the surface temperature of the fabric is within the above range, damage to the inkjet head and the fabric can be reduced. Also, the ink composition is more likely to spread uniformly and penetrate easily on the fabric.

[0162] The surface temperature of the fabric can be measured using, for example, a non-contact thermometer (product name "IT2-80", manufactured by Keyence Corporation).

[0163] In the direct printing recording method, the heating time is preferably, for example, 5 seconds to 5 minutes. If the heating time is within the above range, damage to the inkjet head and fabric will occur. This allows for optimal heating of the fabric while reducing heat transfer.

[0164] 3.4. Washing Process In the printing method according to this embodiment, after the processing liquid composition is applied to the fabric, a washing step may be included as needed. By including a washing step in the printing method, the processing liquid composition and other components that are not attached to the fabric can be removed.

[0165] 4. Examples The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Hereinafter, "%" refers to mass unless otherwise specified.

[0166] 4.1. Preparation of dye printing treatment solution composition Each component was placed in a mixing container to obtain the composition shown in Tables 1 (Figure 1) to 3 (Figure 3) (unit: mass%), mixed and stirred with a magnetic stirrer, and then filtered through a membrane filter with a pore size of 5 μm to obtain treatment liquid compositions 1 to 27.

[0167] The components listed in Tables 1 to 3 are as follows:

[0168] <Resin> • KT-0507: Product name "Elitel (registered trademark) KT-0507", manufactured by Unitika Ltd., polyester resin • KT-8701: Product name "Elitel (registered trademark) KT-8701", manufactured by Unitika Ltd., polyester resin • KT-8803: Product name "Elitel (registered trademark) KT-8803", manufactured by Unitika Ltd., polyester resin <Crosslinking agent> • #220: Product name "Fixer #220", manufactured by Murayama Chemical Research Institute Co., Ltd., isocyanate compound • WS-500: Product name "Epocross (registered trademark) WS-500", manufactured by Nippon Shokubai Co., Ltd., oxazoline compound. <Additives> • GP-250: Product name "Sannix (registered trademark) GP-250", manufactured by Sanyo Chemical Industries, Ltd., polyoxypropylene-glyceryl ether • GP-400: Product name "Sannix (registered trademark) GP-400", manufactured by Sanyo Chemical Industries, Ltd., polyoxypropylene-glyceryl ether • GP-600: Product name "Sannix (registered trademark) GP-600", manufactured by Sanyo Chemical Industries, Ltd., polyoxypropylene-glyceryl ether • PE-61: Product name "Newport (registered trademark) PE-61", manufactured by Sanyo Chemical Industries, Ltd., polyoxyethylene polyoxypropylene block polymer. • PE-71: Product name "Newport (registered trademark) PE-61", manufactured by Sanyo Chemical Industries, Ltd., polyoxyethylene polyoxypropylene block polymer • G-450: Product name "Uniox (registered trademark) G-450", manufactured by NOF Corporation, polyoxyethylene-glyceryl ether • S-753: Product name "WILBRIDE (registered trademark) S-753", manufactured by NOF Corporation, polyoxybutylene polyoxyethylene polyoxypropylene-glyceryl ether • TG-1000R: Product name "Uniol (registered trademark) TG-1000R", manufactured by NOF Corporation, polyoxypropylene-glyceryl ether • SC-P750: Product name, manufactured by Sakamoto Pharmaceutical Co., Ltd., polyoxypropylene-polyglyceryl ether <Thickening agent> • 621TF: Product name "SN Thickener 621TF", manufactured by Sunopco Corporation, urethane-modified polyether <Organic solvents> · 1,2-Hexanediol Glycerin

[0169] 4.2 Preparation of inkjet ink composition The components were put into a mixing vessel so as to have the composition shown in Table 4 (Figure 4) (unit: mass %), mixed and stirred for 2 hours with a magnetic stirrer, and then filtered through a membrane filter with a pore size of 5 μm to obtain an inkjet ink composition (hereinafter, also referred to as "C ink").

[0170] Each component in Table 4 is as follows.

[0171] <Disperse dye> ·Disperse Blue 359: C.I. Disperse Blue 359 (commercially available product) <Water-soluble organic solvent> ·Propylene glycol ·Glycerin ·Methyl triglycol <Surfactant> ·BYK-348: Trade name, manufactured by BYK Chemie Japan Co., Ltd., silicone-based surfactant

[0172] 4.3. Preparation of printed matter 4.3.1. Preparation of cloth with treatment liquid composition attached Treatment liquids 1 to 27 were each attached to cloth to obtain cloth with the treatment liquid composition attached.

[0173] Specifically, as the cloth, white cotton blade #4000 (trade name, manufactured by Toyobo Co., Ltd.) was used. The white cotton blade was immersed in the treatment liquid composition, squeezed using a mangle roller so that the squeezing ratio was 80%, and the treatment liquid composition was attached. Then, after drying at 140 °C for 2 minutes and further drying at 170 °C for 1 minute, cloth with the treatment liquid composition attached was obtained.

[0174] The squeezing ratio (S) was calculated by the following formula (1).

[0175] S (%) = [(A - B) / B] × 100 ··· (1) In formula (1), S represents the squeezing ratio (%), A represents the mass (g) of the cloth with the treatment liquid composition attached, and B represents the mass (g) of the cloth before the treatment liquid composition is attached.

[0176] 4.3.2. Preparation of an intermediate recording medium to which an ink composition is attached. The C ink prepared above was filled into the cartridge of an inkjet printer PX-G930 (product name manufactured by Seiko Epson). Subsequently, on the coated surface of coated paper (TRANSJET Sportsline 1254, product name manufactured by Cham Paper) used as an intermediate transfer medium, an ink injection rate of 12 mg / inch was achieved at a resolution of 720 dpi x 720 dpi and an ink ejection rate of 100% duty cycle. 2 An image having a filled pattern was formed under these conditions. This resulted in obtaining an intermediate recording medium to which the ink composition was attached.

[0177] 4.3.3. Printing The cotton braid to which the processing liquid composition obtained in section 4.3.1. Preparation of fabric with processing liquid composition attached was attached, and the surface on which the image of the intermediate recording medium to which the ink composition obtained in section 4.3.2. Preparation of intermediate recording medium with ink composition attached was formed was then heated using a heat press machine TP-608M (product name of Taiyo Seiki Co., Ltd.) at a temperature of 200°C and a pressure of 4.2 N / cm². 2 The fabric was then heat-transferred under conditions of 60 seconds to obtain printed materials, which were fabrics to which C ink had been applied.

[0178] 4.4. Evaluation of printed materials 4.4.1. Color development The color intensity (hereinafter also referred to as "OD value") of the prints obtained in Examples 1 to 24 and Comparative Examples 1 to 3 with respect to C ink was measured immediately after printing using a fluorescence spectrometer FD-7 (manufactured by Konica Minolta). The measurement conditions were as follows. The measurements were performed at room temperature of 25°C.

[0179] (Measurement conditions) • Observation light source: D65 • Field of view: 2 degrees • Concentration status: T • Polarizing filter: Not installed Furthermore, the evaluation criteria were as follows, and the evaluation results are shown in Tables 5 (Figure 5) to 7 (Figure 7). A rating of C or higher was considered to indicate good color development.

[0180] (Evaluation Criteria) A: OD value is 1.3 or higher B: OD value is 1.2 or higher and less than 1.3 C:OD value is between 1.1 and less than 1.2 D:OD value is 1.0 or greater and less than 1.1 E:OD value less than 1.0

[0181] 4.4.2. Pretreatment marks The fabric was pre-treated using treatment solutions 1 to 27, and the printed material after heat transfer was evaluated. Specifically, a white T-shirt (00085-CVT, product name manufactured by Toms Co., Ltd.) was used as the fabric. The white T-shirt was immersed in the treatment solution composition, and squeezed using a mangle roller to a wringing ratio of 80%, thereby adhering the treatment solution composition. After drying at 140°C for 2 minutes, it was further dried at 170°C for 1 minute to obtain a white T-shirt with the treatment solution composition attached.

[0182] The image-formed surface of the intermediate recording medium prepared in the section "4.3.2. Preparation of an Intermediate Recording Medium with Ink Composition Adhered" described above was heat-transferred onto a white T-shirt to which the processing liquid composition had been applied, thereby obtaining a printed object with C ink adhered to it. The heat transfer was performed using a heat press machine TP-608M (manufactured by Taiyo Seiki Co., Ltd., product name) at a temperature of 200°C and a pressure of 4.2 N / cm². 2 The procedure was performed under conditions of a 60-second transfer time.

[0183] Based on the above, the printed materials of Examples 1 to 24 and Comparative Examples 1 to 3 were obtained.

[0184] The pretreatment traces were evaluated using the prints obtained from Examples 1-24 and Comparative Examples 1-3. Specifically, the L, a*, and b* values ​​of the pretreated and untreated portions of the prints were measured using a fluorescence spectrometer FD-7 (Konica Minolta). The color change ΔE value was calculated using the obtained L, a*, and b* values. The measurement was performed as described in "4.4.1. The same conditions as those used in the "Chromaticity" section were employed, and the experiment was conducted at room temperature of 25°C.

[0185] The evaluation criteria were as follows, and the evaluation results are shown in Tables 5 (Figure 5) to 7 (Figure 7).

[0186] (Evaluation Criteria) A: ΔE is greater than or equal to 0 and less than 1.0 B: ΔE is between 1.0 and less than 2.0 C: ΔE is between 2.0 and less than 3.0 D: ΔE is between 3.0 and 4.0 E:ΔE is 4.0 or higher

[0187] 4.4.3. Fading over time The OD value of the recording surface of the printed material immediately after printing was measured using a fluorescence spectrophotometer FD-7 (Konica Minolta). The recording surface of the printed material was similarly measured the following day, and the rate of change in OD value over time (hereinafter also referred to as "time-dependent fading rate") was calculated. The measurements were performed under the same conditions as described in section 4.4.1, "Color Development," at a room temperature of 25°C.

[0188] The rate of fading over time was calculated using the following formula (2).

[0189] Fading rate over time = (OD value the day after printing) / (OD value immediately after printing) - 1 ... (2) The evaluation criteria were as follows, and the evaluation results are shown in Tables 5 (Figure 5) to 7 (Figure 7).

[0190] (Evaluation Criteria) A: Fading rate over time is -1% or more B: Fading rate over time is between -2% and -1%. C: Fading rate over time is between -4% and -2%. D: Fading rate over time is between -6% and -4%. E: Fading rate over time is less than -6%

[0191] 4.4.4. Evaluation Results The following was found from the experimental and comparative examples.

[0192] Examples relating to a dye printing treatment solution composition comprising a resin, a crosslinking agent, an additive, and water, wherein the additive comprises a compound having a polyoxyalkylene structure, and the compound having a polyoxyalkylene structure is one or more selected from polyoxyalkylene-glyceryl ether, polyoxyalkylene-polyglyceryl ether, and polyoxyalkylene block polymer, showed good results in the evaluation items of color development and pretreatment marks.

[0193] In contrast, the comparative examples that did not meet the above conditions all failed to obtain good results in either color development or pretreatment residue.

[0194] A comparison of Experimental Example 1 and Comparative Example 1 showed that the inclusion of additives in the treatment solution composition resulted in better color development of the printed material and reduced the occurrence of pretreatment marks.

[0195] Furthermore, a comparison of Example 1 with Comparative Examples 2 and 3 showed that including a compound having a polyoxyalkylene structure as an additive resulted in better color development of the printed material.

[0196] Examples 1, 10, and 24 show that when one or more additives selected from polyoxyalkylene-glyceryl ether, polyoxyalkylene-polyglyceryl ether, and polyoxyalkylene block polymer are included, the printed material exhibits good color development and pretreatment marks are eliminated. The occurrence has decreased.

[0197] Examples 1 to 9 showed that when the content of compounds having a polyoxyalkylene structure was within a predetermined range, the printed material tended to exhibit good color development and pretreatment marks were reduced.

[0198] Examples 1, 10, and 11 showed that when the additive contained a predetermined number or more hydroxyl groups, the printed material tended to exhibit good color development.

[0199] Examples 12 and 13 showed that when the number of carbon atoms in the oxyalkylene group of a compound having a polyoxyalkylene structure is within a predetermined range, the printed material exhibits good color development and the occurrence of pretreatment marks tends to be reduced.

[0200] From Example 13, when the additive had a polyoxyalkylene structure with oxyalkylene groups having different numbers of carbon atoms in the molecule, the printed material showed good color development and reduced fading over time. In addition, there was a tendency for the occurrence of pretreatment marks to be reduced.

[0201] Examples 1 and 14 showed that when the number-average molecular weight of the compound having a polyoxyalkylene structure was within a predetermined range, the printed material exhibited good color development and reduced fading over time. Furthermore, the occurrence of pretreatment marks tended to be reduced.

[0202] Examples 1 and 15 showed that the inclusion of an organic solvent resulted in better color development of the printed material and reduced fading over time. Furthermore, the occurrence of pretreatment marks tended to decrease.

[0203] Examples 16 and 17 showed that when the resin content was within a predetermined range in terms of solid content, the occurrence of pretreatment marks on the printed material was reduced, and fading over time also tended to be reduced.

[0204] Furthermore, Examples 16 and 17 showed that when the crosslinking agent content was within a predetermined range in terms of solid content, the occurrence of pretreatment marks on the printed material was reduced, and fading over time also tended to be reduced.

[0205] Examples 1, 18, and 19 showed that when the glass transition temperature of the resin was above a predetermined value, the occurrence of pretreatment marks tended to decrease.

[0206] Examples 1 and 20 showed that when the crosslinking agent was an isocyanate compound and had an isocyanurate skeleton in its structure, the printed material tended to exhibit good color development and reduced fading over time.

[0207] Examples 21-24 showed that various combinations of polyoxyalkylene-glyceryl ether, polyoxyalkylene-polyglyceryl ether, and polyoxyalkylene block polymer as additives tended to reduce the occurrence of pretreatment marks and the fading of printed materials over time.

[0208] The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes configurations that are substantially identical to the configurations described in the embodiments, for example, configurations that have the same function, method and result, or configurations that have the same purpose and effect. The present invention also includes configurations in which non-essential parts of the configurations described in the embodiments are replaced. Furthermore, the present invention includes configurations that produce the same effects or achieve the same purpose as the configurations described in the embodiments. Furthermore, the present invention includes configurations that add known technology to the configurations described in the embodiments.

[0209] From the embodiments and modifications described above, the following can be derived.

[0210] Dye printing treatment solution composition, It contains resin, crosslinking agent, additives, and water. The aforementioned additive includes a compound having a polyoxyalkylene structure. The compound having the polyoxyalkylene structure is one or more selected from polyoxyalkylene-glyceryl ether, polyoxyalkylene-polyglyceryl ether, and polyoxyalkylene block polymer.

[0211] This dye printing treatment solution composition contains one or more additives selected from polyoxyalkylene-glyceryl ether, polyoxyalkylene-polyglyceryl ether, and polyoxyalkylene block polymer as compounds having a polyoxyalkylene structure. This improves the viscosity of the treatment solution composition, reduces the movement and localization of potassium and sodium ions, which cause pretreatment marks, and thus reduces the occurrence of pretreatment marks. Furthermore, the additives make the dyes easier to dissolve or decompose, allowing the dyes to penetrate deep into the fabric, resulting in prints that exhibit good color development.

[0212] In the above-described dye printing treatment solution composition, the compound having the polyoxyalkylene structure may have 2 to 4 carbon atoms in the oxyalkylene group.

[0213] According to this dye printing treatment solution composition, when the compound having a polyoxyalkylene structure has 2 to 4 carbon atoms in the oxyalkylene group, the printed material exhibits good color development and pretreatment marks are reduced.

[0214] In the above-described dye printing treatment solution composition, the additive may include a compound having the polyoxyalkylene structure, which has oxyalkylene groups with different numbers of carbon atoms in its molecule.

[0215] According to this dye printing treatment solution composition, when a compound having a polyoxyalkylene structure has oxyalkylene groups with different numbers of carbon atoms in its molecule, the printed material exhibits good color development and reduced fading over time. Furthermore, the occurrence of pre-treatment marks is also reduced.

[0216] In the above-described dye printing treatment solution composition, the additive may include a compound having three or more hydroxyl groups.

[0217] According to this dye printing treatment solution composition, if the additive contains a compound with three or more hydroxyl groups, the printed material exhibits good color development.

[0218] In the above-described dye printing treatment solution composition, the number-average molecular weight of the compound having the polyoxyalkylene structure may be 250 or more and 1000 or less.

[0219] According to this dye printing treatment solution composition, when the number-average molecular weight of the compound having a polyoxyalkylene structure is between 250 and 1000, the printed material exhibits good color development and reduced fading over time. Furthermore, the occurrence of pre-treatment marks is reduced.

[0220] In the above-described dye printing treatment liquid composition, the resin may be a polyester resin.

[0221] According to this dye printing treatment solution composition, when the resin is a polyester resin, the printed material exhibits good color development and texture.

[0222] In the above dye printing treatment liquid composition, the glass transition temperature of the resin is 25°C or higher. It's okay to have it.

[0223] According to this dye printing treatment solution composition, when the glass transition temperature of the resin is 25°C or higher, the printed material exhibits good color development and the occurrence of pretreatment marks is reduced.

[0224] In the above-described dye printing treatment liquid composition, the resin content may be 2% by mass or more and 20% by mass or less in terms of solid content relative to the total amount of the dye printing treatment liquid composition.

[0225] This dye-based printing treatment solution composition reduces the occurrence of pre-treatment marks. It also reduces the fading of printed materials over time.

[0226] In the above-described dye printing treatment solution composition, the crosslinking agent may be an isocyanate compound.

[0227] This dye printing treatment solution composition produces printed materials with good color development and reduces fading over time.

[0228] In the above-described dye printing treatment solution composition, the crosslinking agent may be an isocyanate compound having an isocyanurate skeleton in its structure.

[0229] This dye printing treatment solution composition produces printed materials with good color development and reduces fading over time.

[0230] In the above-described dye printing treatment solution composition, the content of the crosslinking agent may be 1% by mass or more and 3% by mass or less in terms of solid content relative to the total amount of the dye printing treatment solution composition.

[0231] This dye printing treatment solution composition produces printed materials with good color development and reduces fading over time.

[0232] The above-described dye printing treatment solution composition may further contain an organic solvent.

[0233] This dye-based printing treatment solution composition results in printed materials exhibiting good color development and reduced fading over time. Furthermore, it reduces the occurrence of pre-treatment marks.

[0234] The composition set comprises the above-described dye printing treatment liquid composition and an inkjet ink composition, wherein the inkjet ink composition may contain a disperse dye and water.

[0235] This composition set results in printed materials exhibiting good color development and reduced fading over time. Furthermore, it reduces the occurrence of pre-treatment marks.

[0236] The printing method may include a step of applying the above-mentioned dye printing treatment solution composition to the fabric.

[0237] This printing method results in prints with good color development and reduces the occurrence of pre-treatment marks.

[0238] In the above-described printing method, a drying step may be included after the step of applying the processing liquid composition to the fabric, in which the dye printing processing liquid composition applied to the fabric is dried.

[0239] This printing method results in prints with good color development and reduces the occurrence of pre-treatment marks.

[0240] In the above-described printing method, a heat press method may be used in the drying step.

[0241] This printing method results in prints with good color development and reduces the occurrence of pre-treatment marks.

[0242] In the above-described printing method, the fabric may contain fibers having hydroxyl groups.

[0243] This printing method produces printed materials with excellent color development and reduces fading over time.

[0244] In the above-described printing method, the fabric is white cotton, and the fabric may be in the form of a T-shirt.

[0245] This printing method produces printed materials with excellent color development and reduces fading over time.

Claims

1. It contains resin, crosslinking agent, additives, and water. The aforementioned additive includes a compound having a polyoxyalkylene structure. The compound having the polyoxyalkylene structure is one or more selected from polyoxyalkylene-glyceryl ether, polyoxyalkylene-polyglyceryl ether, and polyoxyalkylene block polymer, in a dye printing treatment solution composition.

2. The dye printing treatment solution composition according to claim 1, wherein the compound having the polyoxyalkylene structure has 2 to 4 carbon atoms in the oxyalkylene group.

3. The dye printing treatment solution composition according to claim 1, wherein the additive comprises a compound having the polyoxyalkylene structure, which has oxyalkylene groups with different numbers of carbon atoms in its molecule.

4. The dye printing treatment solution composition according to claim 1, wherein the additive comprises a compound having three or more hydroxyl groups.

5. The dye printing treatment solution composition according to claim 1, wherein the number average molecular weight of the compound having the polyoxyalkylene structure is 250 or more and 1000 or less.

6. The dye printing treatment liquid composition according to claim 1, wherein the resin is a polyester resin.

7. The dye printing treatment liquid composition according to claim 1, wherein the glass transition temperature of the resin is 25°C or higher.

8. The content of the resin is 2% by mass or more and 20% by mass or less in terms of solid content, relative to the total amount of the dye printing treatment solution composition, as described in claim 1.

9. The dye printing treatment solution composition according to claim 1, wherein the crosslinking agent is an isocyanate compound.

10. The isocyanate compound has an isocyanurate skeleton in its structure, as described in claim 9, for use as a dye printing treatment solution composition.

11. The dye printing treatment solution composition according to claim 1, wherein the content of the crosslinking agent is 1% by mass or more and 3% by mass or less on a solid content basis with respect to the total amount of the dye printing treatment solution composition.

12. The dye printing treatment liquid composition according to claim 1, further comprising an organic solvent.

13. A dye printing treatment solution composition according to any one of claims 1 to 12, Inkjet ink composition and Equipped with, A composition set comprising the inkjet ink composition, a disperse dye, and water.

14. A printing method comprising a step of applying a dye printing treatment solution composition according to any one of claims 1 to 12 to a fabric.

15. The printing method according to claim 14, further comprising a drying step of drying the dye printing processing liquid composition that has been applied to the fabric after the processing liquid composition application step.

16. The printing method according to claim 15, wherein a heat press method is used in the drying step.

17. The printing method according to claim 14, wherein the fabric comprises fibers having hydroxyl groups.

18. The printing method according to claim 17, wherein the fabric is white cotton and the fabric is in the form of a T-shirt.

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