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

Abstract

To provide a printed textile having excellent color development properties and dry cleaning resistance, obtained by attaching a treatment liquid composition to a fabric in advance, and subjecting the fabric having the treatment liquid composition attached thereto to dye printing.SOLUTION: A treatment liquid composition for dye printing according to the present disclosure is used in a state of being attached to a fabric and includes resin particles, a crosslinking agent, an organic solvent, and water, in which the organic solvent has an SP value of 13.5 or less, the organic solvent has a standard boiling point of 100°C or higher, and the content of the organic solvent is 5 mass% or more with respect to the total amount of the treatment liquid composition.SELECTED DRAWING: Figure 1

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 produce printed materials, a technique is known in which the fabric is pre-treated using a treatment solution to improve the color development and dry cleaning resistance of the colorant. As an example of such a technique, Patent Document 1 describes a technique in which a sheet-like structure is impregnated with an aqueous liquid containing an organic solvent that can be miscible with water boiling at 140°C or higher for disperse dyes, a crosslinking agent, and a high polymer that can be dyed with disperse dyes and fixed to a fiber material, dried, and then printed by heat transfer. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 52-70183 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, the aqueous liquid described in Patent Document 1 has high penetration into the fabric, making it difficult for the treatment solution to remain near the fabric. Therefore, using the aqueous liquid described in Patent Document 1 does not yield the desired effect of modifying the fabric with the treatment solution, resulting in the problem of not being able to obtain printed materials with excellent color development and dry cleaning resistance. [Means for solving the problem]

[0005] The present invention is a treatment liquid composition to be used by being attached to a fabric, the composition comprising resin particles, a crosslinking agent, an organic solvent, and water, wherein the SP value of the organic solvent is 13.5 or less, the normal boiling point of the organic solvent is 100°C or higher, and the content of the organic solvent is 5 mass% or more relative to the total amount of the treatment liquid composition, which is a treatment liquid composition for dye textile printing. [Brief Description of the Drawings]

[0006] [Figure 1] This is a flowchart showing an example of the indirect textile printing recording method of the present embodiment. [Mode for Carrying Out the Invention]

[0007] Hereinafter, the embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications are possible without departing from the gist thereof.

[0008] 1. Treatment liquid composition for dye textile printing The treatment liquid composition for dye textile printing of the present embodiment (hereinafter also referred to as "the treatment liquid composition") is a treatment liquid composition to be used by being attached to a fabric, and comprises resin particles, a crosslinking agent, an organic solvent, and water, wherein the SP value of the organic solvent is 13.5 or less, the normal boiling point of the organic solvent is 100°C or higher, and the content of the organic solvent is 5 mass% or more relative to the total amount of the treatment liquid composition. The treatment liquid composition is preferably used to be attached to the fabric before performing dye textile printing on the fabric.

[0009] According to the present embodiment, by attaching the treatment liquid composition to the fabric in advance and performing dye textile printing on the fabric to which the treatment liquid composition has been attached, a printed matter having excellent color developability and dry cleaning resistance can be obtained.

[0010] Although the reason why such excellent effects are obtained by the present embodiment is not certain, the present inventors presume as follows. That is, usually, since fabrics have high permeability to treatment liquid compositions, the treatment liquid hardly stays in the vicinity of the fabric. For this reason, it is difficult to obtain the effect of the treatment liquid, that is, modification of the fabric by the treatment liquid, so the obtained printed matter tends to be inferior in color developability and dry cleaning resistance. However, the treatment liquid composition of the present embodiment contains resin particles, a crosslinking agent, an organic solvent, and water, wherein the SP value of the organic solvent is 13.5 or less, the normal boiling point of the organic solvent is 100°C or higher, and the content of the organic solvent is 5% by mass or more relative to the total amount of the treatment liquid composition. When the treatment liquid composition contains a specific organic solvent in a specific amount, the permeability of the fabric to the treatment liquid is reduced, and the treatment liquid easily stays in the vicinity of the fabric. In addition, since the organic solvent according to the present embodiment has a high boiling point, the organic solvent hardly volatilizes even during heating at the time of drying after the treatment liquid composition is adhered to the fabric or at the time of image transfer, and can stay in the vicinity of the fabric. Furthermore, since the SP value of the organic solvent falls within a specific range, the compatibility with the oil-soluble dye contained in the ink composition is relatively high. Therefore, the dye can be favorably dissolved in the organic solvent remaining in the vicinity of the fabric to develop color. Moreover, since the treatment liquid composition contains resin particles and a crosslinking agent, the dye dissolved in the organic solvent also dyes the resin particles, and the dyed resin particles are favorably bound to the fabric by the crosslinking agent. For these reasons, by adhering the treatment liquid composition of the present embodiment to a fabric and performing dye printing, a large amount of ink can be adhered to the vicinity of the fabric. Therefore, it is estimated that a printed matter having excellent color developability and dry cleaning resistance can be obtained. However, the reason is not limited to this.

[0011] Next, each component contained in the treatment liquid composition and the ink composition will be described.

[0012] 1.1. Resin The treatment liquid composition contains resin particles. When the treatment liquid composition contains resin particles, a printed matter having excellent color developability and dry cleaning resistance can be obtained.

[0013] Examples of resin particles include polyester resins, urethane resins, addition polymerization resins, fluororesins, and natural resins. These resin particles are often handled in emulsion form, i.e., resin dispersions, but may also be supplied in powder form. Furthermore, the resin particles can be used individually or in combination of two or more types.

[0014] In order to obtain an imprinted product that has a good balance of wash fastness and texture, as well as superior color development and dry cleaning resistance, the resin particles preferably contain one or more selected from the group consisting of polyester resins and urethane resins, and more preferably contain polyester resins.

[0015] Examples of polyester resins include resins having structural units derived from polycarboxylic acids and structural units derived from polyhydric alcohols.

[0016] 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, 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.

[0017] 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.

[0018] The polyester resin preferably contains hydroxyl groups, carboxyl groups, and sulfonic acid groups, as well as their sodium salts. These groups may be present in the polyester resin in one or more types.

[0019] A sulfonic acid group-containing polyester resin, for example, has constituent units derived from a polyhydric carboxylic acid, constituent units derived from a polyhydric alcohol, and constituent units derived from a sulfonic acid group-containing aromatic monomer. 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. The salts may be selected based on the above, with sodium salts being preferred.

[0020] By including these groups in the polyester resin, the polyester resin can react well with the crosslinking agent, preferably with a compound containing an isocyanate group, resulting in good adhesion to fabrics, preferably fabrics containing fibers with hydroxyl groups. Therefore, it becomes possible to obtain printed materials that have an even better balance of wash fastness and texture, while also possessing superior color development and dry cleaning resistance.

[0021] Polyester resins can be obtained, for example, by selecting one or more of the above-mentioned polycarboxylic acids, polyhydric alcohols, and optionally sulfonic acid group-containing aromatic monomers, and synthesizing them by conventional polycondensation reactions.

[0022] Commercially available polyester resins can also be used. Examples of commercially available products include: Elite® KA-5071S, KT-8803, KT-9204, KT-8701, KT-8904, and KT-0507 (all trade names, Unitika Ltd., polyester resin emulsion); Hi-Tec® SN-2002 (trade name, Toho Chemical Industry Co., Ltd., polyester resin emulsion); and Pluscoat (registered trademark). Examples include 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 (registered trademark) MD-1200, MD-1500, and MD-2000 (all trade names, manufactured by Toyobo Co., Ltd.).

[0023] Urethane resins are a general term for resins that contain urethane bonds. Examples of urethane resins include polyether-type urethane resins that contain ether bonds in the main chain in addition to urethane bonds, polyester-type urethane resins that contain ester bonds in the main chain, and polycarbonate-type urethane resins that contain carbonate bonds in the main chain. Furthermore, commercially available urethane resins may be used, such as Superflex® 460, 460s, 840, E-4000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Rezamin® D-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (manufactured by Dainichi Seika Kogyo Co., Ltd.), Takelac® W-6061, WS-6021, W-512-A-6 (manufactured by Mitsui Chemicals, Inc.), SunCure® 2710 (manufactured by Lubrizol Inc.), and Permarin® UA-150 (manufactured by Sanyo Chemical Industries, Ltd.).

[0024] Examples of addition polymerization resins include homopolymers or copolymers of (meth)acrylic acid, (meth)acrylic acid esters, acrylonitrile, cyanoacrylate, acrylamide, olefin, styrene, silicone, rosin, terpene, epoxy, polyester, vinyl acetate, vinyl chloride, vinyl alcohol, vinyl ether, vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinylimidazole, and vinylidene chloride.

[0025] Other commercially available emulsion forms include, for example, Vinibran® 150, 603, 745, 1245L (manufactured by Nisshin Chemical Industry Co., Ltd.), Danfix® MM11 (manufactured by Nisshin Chemical Industry Co., Ltd.), Senka Antiflick® CX-2 (manufactured by Senka Co., Ltd.), Movinyl® 966A (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and Microgel® E- 1002, E-5002 (manufactured by Nippon Paint Co., Ltd.), Boncoat (registered trademark) 4001, 5454 (manufactured by DIC Corporation), SAE1014 (manufactured by Nippon Zeon Co., Ltd.), Saibinol (registered trademark) SK-200 (manufactured by Saiden Chemical Co., Ltd.), Joncryl (registered trademark) 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, 7610 (manufactured by BASF), NK Binder R-5HN (manufactured by Shin Nakamura Chemical Co., Ltd.), SanCure 2710 (manufactured by Nippon Lubrizol Co., Ltd.), Permarin® UA-150 (manufactured by Sanyo Chemical Industries, Ltd.) Examples include Superflex® 460, 470, 610, 700 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), NeoRez® R-9660, R-9637, R-940 (manufactured by Kusumoto Kasei Co., Ltd.), Adekabon Titer® HUX-380, 290K (manufactured by ADEKA Corporation), and Takelac® W-605, W-635, WS-6021 (manufactured by Mitsui Chemicals, Inc.).

[0026] Although commercially available products are listed above, resin particles may also be obtained by synthesis using conventional methods.

[0027] To obtain an imprint with superior color development and dry cleaning resistance, as well as a better balance of wash fastness and texture, it is preferable that the resin particle content be 1% to 20% by mass in terms of solid content relative to the total amount of the processing liquid composition. Furthermore, to obtain an imprint with even better color development and dry cleaning resistance, as well as a better balance of wash fastness and texture, it is more preferable that the resin particle content be 2% to 15% by mass, and more preferably 2% to 10% by mass, relative to the total amount of the processing liquid composition in terms of solid content.

[0028] 1.2. Crosslinking Agents The processing solution composition contains a crosslinking agent. By including a crosslinking agent in the treatment solution composition, crosslinking properties can be imparted to the composition, making it possible to bind resin particles, dyes, and fabrics together. As a result, printed materials with excellent color development and dry cleaning resistance can be obtained.

[0029] 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.

[0030] Since it is possible to obtain printed fabrics that have a better balance of wash fastness and texture, as well as superior color development and dry cleaning resistance, it is preferable that the crosslinking agent contains one or more compounds selected from the group consisting of compounds containing isocyanate groups and compounds containing oxazoline groups, and it is more preferable that it contains compounds containing isocyanate groups.

[0031] Examples of compounds containing isocyanate groups include water-dispersible (blocked) polyisocyanates. (Blocked) polyisocyanate refers to polyisocyanate and / or blocked polyisocyanate. These isocyanate group-containing compounds may be used individually or in combination of two or more.

[0032] 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.

[0033] 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. Furthermore, polyisocyanates may have an isocyanurate skeleton in their structure. These polyisocyanates may be used individually or in combination of two or more.

[0034] 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.

[0035] The crosslinking agent is preferably a compound containing isocyanate groups having an isocyanurate skeleton in its structure, and more preferably a water-dispersible polyisocyanate having an isocyanurate skeleton in its structure. Compounds containing isocyanate groups having an isocyanurate skeleton tend to have at least three crosslinking sites, which can improve the binding between the resin particles and the fabric. As a result, it is possible to obtain printed fabrics that have an even better balance of wash fastness and texture, as well as even better color development and dry cleaning resistance.

[0036] Commercially available compounds containing such 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.).

[0037] Examples of compounds 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.

[0038] Since printed fabrics that have well-balanced washing fastness and texture properties, as well as more excellent color development properties and dry cleaning resistance tend to be obtained, the oxazoline group-containing compound preferably includes a water-soluble oxazoline group-containing compound.

[0039] As such an oxazoline group-containing compound, a commercially available product can also be used. Examples of commercially available products include Epocros (registered trademark) K-2010, K-2020, K-2030, K-2035E, WS-300, WS-500, and WS-700 (all the above are trade names, manufactured by Nippon Shokubai Co., Ltd.).

[0040] The crosslinking agent may be used alone, or two or more thereof may be used in combination.

[0041] Since printed fabrics that have further well-balanced washing fastness and texture properties, as well as further excellent color development properties and dry cleaning resistance tend to be obtained, the content of the crosslinking agent is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.5% by mass or more and 3% by mass or less, in terms of solid content, relative to the total amount of the treatment liquid composition.

[0042] 1.3. Organic Solvent The treatment liquid composition contains an organic solvent. The SP value of the organic solvent is 13.5 or less, and the normal boiling point of the organic solvent (hereinafter also referred to as "b.p.") is 100°C or higher (hereinafter also referred to as "specific organic solvent"). The specific organic solvent can be used singly or in combination of two or more kinds.

[0043] In the present specification, the SP value is a solubility parameter based on the Hansen method, and is also referred to as Hansen SP value. The Hansen method classifies the SP value δ into three terms, and δ 2 =δ d 2 +δ p 2 +δ h 2 is expressed and calculated as follows. δ d , δ p, δ h These are solubility parameters corresponding to the dispersion force term, the inter-dipole force term, and the hydrogen bonding force term, respectively. The units for SP value and Hansen SP value are (cal / cm²). 3 ) 1 / 2 The Hansen SP value may be the value derived using the calculation software Hansen-Solubility HSPiP.

[0044] In this specification, the standard boiling point means the boiling point at a standard atmospheric pressure of 1013.25 hPa.

[0045] In this embodiment, by using a specific organic solvent, the water absorption behavior of the fabric can be mitigated, reducing the penetration of the treatment solution composition into the fabric, which allows the treatment solution to remain near the fabric. Furthermore, since the specific organic solvent has an SP value of 13.5 or less, it has relatively high compatibility with the dye contained in the ink composition. Therefore, the dye can be suitably dissolved in the organic solvent remaining near the fabric, and the resin particles can be suitably dyed near the fabric.

[0046] Since it is possible to obtain printed fabrics that have a better balance of wash fastness and texture, as well as superior color development and dry cleaning resistance, the lower limit of the SP value of the organic solvent is preferably 7.0 or higher, and more preferably 8.0 or higher.

[0047] Since it is possible to obtain printed fabrics that have a better balance of wash fastness and texture, as well as superior color development and dry cleaning resistance, the upper limit of the standard boiling point of the organic solvent is preferably 300°C or lower, and more preferably 289°C or lower.

[0048] The specific organic solvent is not particularly limited, as long as it has an SP value of 13.5 or less and a standard boiling point of 100°C or higher. Examples of such specific organic solvents include glycols, glycol ethers, nitrogen-containing solvents, esters, cyclic esters, and monools, all of which have an SP value of 13.5 or less and a standard boiling point of 100°C or higher. It is preferable that the specific organic solvent includes one or more selected from the group consisting of glycols, glycol ethers, and nitrogen-containing solvents, all of which have an SP value of 13.5 or less and a standard boiling point of 100°C or higher, as this tends to result in printed materials with a better balance of wash fastness and texture, while also possessing superior color development and dry-cleaning resistance.

[0049] Examples of glycols with an SP value of 13.5 or less and a standard boiling point of 100°C or higher include triethylene glycol (SP value: 13.5, standard boiling point: 287°C), 1,2-hexanediol (SP value: 12.1, standard boiling point: 170°C), diethylene glycol (SP value: 12.1, standard boiling point: 245°C), dipropylene glycol (SP value: 12.1, standard boiling point: 231°C), 1,3-butanediol (SP value: 11.6, standard boiling point: 207°C), 1,6-hexanediol (SP value: 12.3, standard boiling point: 250°C), tetraethylene glycol (SP value: 12.3, standard boiling point: 314°C), and 2-ethyl-1,3-hexanediol (SP value: 11.3, standard boiling point: 244°C).

[0050] Examples of glycol ethers with an SP value of 13.5 or less and a standard boiling point of 100°C or higher include dipropylene glycol monomethyl ether (SP value: 10.1, standard boiling point: 188°C), dipropylene glycol dimethyl ether (SP value: 8.4, standard boiling point: 171°C), triethylene glycol monobutyl ether (SP value: 10.0, standard boiling point: 278°C), ethylene glycol diethyl ether (SP value: 8.3, standard boiling point: 189°C), ethylene glycol monoethyl ether (SP value: 10.5, standard boiling point: 135°C), ethylene glycol monophenyl ether (SP value: 11.5, standard boiling point: 245°C), and ethylene glycol monoethyl ether. Examples include ethylene glycol monobutyl ether (SP value: 9.5, standard boiling point: 171°C), ethylene glycol monobenzyl ether (SP value: 10.9, standard boiling point: 256°C), ethylene glycol monomethyl ether (SP value: 11.4, standard boiling point: 124°C), diethylene glycol monoethyl ether (SP value: 10.2, standard boiling point: 202°C), diethylene glycol monobutyl ether (SP value: 10.0, standard boiling point: 231°C), triethylene glycol monomethyl ether (SP value: 10.5, standard boiling point: 248°C), and propylene glycol monomethyl ether (SP value: 10.0, standard boiling point: 121°C).

[0051] Examples of nitrogen-containing solvents with an SP value of 13.5 or less and a standard boiling point of 100°C or higher include 2-pyrrolidone (SP value: 11.5, standard boiling point: 245°C), dimethylformamide (SP value: 12.2, standard boiling point: 153°C), N-methyl-2-pyrrolidone (SP value: 11.2, standard boiling point: 202°C), and aniline (SP value: 11.6, standard boiling point: 184°C).

[0052] Examples of esters with an SP value of 13.5 or less and a standard boiling point of 100°C or higher include ethylene glycol diacetate (SP value: 10.0, standard boiling point: 190°C), ethylene glycol monomethyl ether acetate (SP value: 9.2, standard boiling point: 145°C), diethylene glycol monobutyl ether acetate (SP value: 8.5, standard boiling point: 246°C), allyl acetate (SP value: 9.2, standard boiling point: 103°C), and butyl acetate (SP value: 8.5, standard boiling point: 126°C).

[0053] Examples of cyclic esters with an SP value of 13.5 or less and a standard boiling point of 100°C or higher include ε-caprolactone (SP value: 10.1, standard boiling point: 241°C).

[0054] Examples of monools with an SP value of 13.5 or less and a standard boiling point of 100°C or higher include 1-butanol (SP value: 11.3, standard boiling point: 118°C), 2-ethyl-1-hexanol (SP value: 9.5, standard boiling point: 185°C), and 3-buten-1-ol (SP value: 11.0, standard boiling point: 114°C).

[0055] Since it is possible to obtain printed fabrics that have an even better balance of wash fastness and texture, as well as even better color development and dry cleaning resistance, it is preferable that the organic solvent contains one or more selected from the group consisting of triethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, triethylene glycol monobutyl ether, and 2-pyrrolidone.

[0056] Since it is possible to obtain printed fabrics that have a better balance of wash fastness and texture, as well as even better color development and dry cleaning resistance, the content of the organic solvent is preferably 5% by mass or more, 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.

[0057] 1.4.Water The processing liquid composition contains water. The water evaporates and dissipates during drying after the treatment solution composition is 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.

[0058] The water content is preferably 30% to 98% by mass, more preferably 35% to 96% by mass, and more preferably 40% to 94% by mass, relative to the total amount of the treatment liquid composition. By setting the water content within the above range, the increase in viscosity of the treatment liquid can be suppressed, improving the workability when applying the treatment liquid to the fabric and the drying properties after application. For fabrics, preferably fabrics containing 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.

[0059] 1.5. Other Organic Solvents The processing liquid composition may contain other organic solvents besides the specific organic solvent, as long as it achieves the effects of the present invention. The other organic solvents are not particularly limited, as long as they have an SP value greater than 13.5 and a standard boiling point less than 100°C. Preferably, the other organic solvents are water-soluble.

[0060] Examples of such water-soluble organic solvents include glycerin; glycols such as ethylene glycol; glycol monoethers such as ethylene glycol monomethyl ether; and alcohols such as methanol and ethanol. Other organic solvents may be used individually or in combination of two or more.

[0061] The content of other organic solvents is usually 20% by mass or less relative to the total amount of the treatment liquid composition, but may be 0.01% by mass or more and 15% by mass or less.

[0062] 1.6. 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.

[0063] The additive content 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.

[0064] 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.

[0065] 1.8. Physical properties of the processing 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.

[0066] 1.8.1.Viscosity The viscosity of the treatment liquid composition at 20°C is preferably between 1.5 mPa·s and 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).

[0067] 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. By setting the surface tension of the treatment liquid composition at 25°C within the above range, appropriate wettability and penetration to the fabric are achieved. Furthermore, since the treatment liquid composition is more easily absorbed uniformly into 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. 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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 because it provides even better dyeability and produces prints with sufficient color development. CI Disperse Red 60 is more preferred as the red dye. CI Disperse Yellow 54 is more preferred as the yellow dye.

[0073] From the viewpoint of achieving the effects of this embodiment more effectively and reliably, the colorant content is preferably 0.05% by mass or more and 20% by mass or less, relative to the total amount of the ink composition.

[0074] 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.

[0075] From the viewpoint of achieving the effects of this embodiment more effectively and reliably, 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] From the viewpoint of achieving the effects of this embodiment more effectively and reliably, the content of the dispersant is preferably 3.0% by mass or more and 8.0% by mass or less, relative to the total amount of the ink composition.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] From the viewpoint of achieving the effects of this embodiment more effectively and reliably, the surfactant content is preferably 0.5% by mass or more and 5.0% by mass or less based on the total amount of the ink composition.

[0088] 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 Examples include glycol monoethers such as methyl glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and methyl triglycerol; 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.

[0089] Glycerin, glycols, and glycol monoethers can primarily function as penetrating solvents and / or humectants. Glycol monoethers tend to have strong penetrating solvent properties, while glycerin and glycols tend to have strong humectant properties.

[0090] 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% by mass or more and 30% by mass or less, relative to the total amount of the ink composition.

[0091] 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.

[0092] 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.

[0093] The additive content is 0.01% by mass or more and 5.0% by mass or less, based on the total amount of the ink composition.

[0094] 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 means 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.

[0095] 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.

[0096] 3. Composition Set The composition set comprises the above-mentioned processing liquid composition and the above-mentioned ink composition.

[0097] In this embodiment, the treatment liquid composition is first applied to the fabric to obtain a fabric to which the treatment liquid composition has been applied. Then, by printing the fabric to which the treatment liquid composition has been applied with the ink composition, it is possible to obtain a printed material that has a good balance of wash fastness and texture, as well as excellent color development and dry cleaning resistance.

[0098] 4.Fabric Examples of fabrics according to this embodiment 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 these fibers.

[0099] To obtain a printed material that has a better balance of wash fastness and texture, as well as superior color development and dry cleaning resistance, it is preferable that the fabric contains fibers having hydroxyl groups, and more preferably cotton. The fibers having hydroxyl groups may be blends thereof.

[0100] 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.

[0101] The weight of the fabric is preferably between 1.0 oz and 10.0 oz. Good recording can be achieved when the fabric weight is within this range.

[0102] As for the fabric, pre-colored fabrics may be used. Since the treatment solution composition is less likely to cause treatment marks, it can be used even with pre-colored fabrics. In other words, even if the fabric is colored, it is possible to perform printing while suppressing the occurrence of treatment marks, thereby improving the quality and commercial value of the printed product compared to conventional methods.

[0103] 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.

[0104] 5. Printing Method 5.1. Process for attaching the treatment liquid composition The printing method of this embodiment includes a step of applying the processing liquid composition to a fabric. This process yields a fabric to which the treatment solution composition has adhered. Furthermore, by applying the ink composition to this fabric, an imprinted material is obtained that has a good balance of wash fastness and texture, while possessing excellent color development and dry cleaning resistance. The printing method can be applied to various fabrics and can produce good print quality.

[0105] 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 2 It is more preferable to apply the treatment solution composition as follows: By setting the amount of treatment solution composition applied 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 improving color development.

[0106] 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.

[0107] 5.2. Drying process In the printing method, it is preferable to include a drying step in which the treatment liquid composition is applied to the fabric, after which the treatment liquid composition applied to the fabric is dried. The drying of the treatment liquid composition may be carried out by natural drying, but it is preferable to dry it with heat in order to improve the amount of treatment liquid composition that adheres to the fabric and to improve the drying speed.

[0108] During the drying process, volatile components such as organic solvents and water contained in the processing liquid composition are evaporated, which tends to result in printed materials that have a better balance of wash fastness and texture, as well as superior color development and dry cleaning resistance. The reason for these excellent effects is not entirely clear, but the inventors of the present invention deduce the following. In other words, by pre-drying the fabric to which the treatment solution composition is attached, and removing some of the volatile components from the fabric, the organic solvent and water become more easily absorbed by the fabric, and the organic solvent can remain more uniformly in the vicinity of the fabric. Here, the sublimable colorant used in this embodiment has a high oil-soluble property. Therefore, it is presumed that in the vicinity of the fabric, the dye dissolves suitably in the organic solvent, resulting in better fixation to the fabric and superior color development. However, the reasons are not limited to this.

[0109] To obtain printed materials that have an even better balance of wash fastness and texture, as well as superior color development and dry cleaning resistance, the drying temperature is preferably 300°C or lower, and more preferably 250°C or lower. Furthermore, by setting the upper limit of the drying temperature within this range, even if the fabric is pre-colored with dye, the sublimation of the dye due to heat drying is suppressed, and the fading of the fabric color of the fabric tends to be suppressed. The lower limit of the heating temperature is preferably 50°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher.

[0110] 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 (lamps), and microwaves.

[0111] The heating time is preferably, for example, between 1 second and 5 minutes. By heating within this range, volatile components such as organic solvents and water can be more effectively evaporated from the fabric, and damage to the fabric tends to be reduced.

[0112] For example, the pressure during heating is 1 N / cm². 3 More than 10N / cm 3 The following is preferable: 3 N / cm 3 More than 6N / cm 3 The following is more preferable: When the drying pressure is within the above range, volatile components such as organic solvents and water can be more effectively evaporated from the fabric, and damage to the fabric tends to be reduced.

[0113] 5.1.1.Drying rate In order to obtain printed materials that have an even better balance of wash fastness and texture, as well as even better color development and dry cleaning resistance, it is preferable that the drying rate of the fabric to which the treatment liquid composition adheres after the drying process is 50% or more and 90% or less, as represented by the following formula (1). Drying rate (%)=[1-[(W B -W0) / W A 〕]×100···(1) In formula (1), W B W0 represents the mass of the fabric with volatile components from the treatment solution composition attached after drying, W0 represents the mass of the untreated fabric, and W A This indicates the mass of the fabric to which volatile components contained in the treatment solution composition have adhered before drying.

[0114] In this specification, the drying rate refers to the degree to which volatile components contained in the treatment liquid composition evaporate from the fabric after they have been attached to the fabric and are dried, and is calculated using the formula (1) above. That is, the drying rate refers to the rate of decrease in the mass of volatile components that have evaporated from the fabric due to drying, from the fabric to which the volatile components were attached. Specifically, for example, a drying rate of 90% means that 90% of the volatile components have evaporated from the fabric due to drying (10% of the volatile components remain in the fabric), and a drying rate of 20% means that 20% of the volatile components have evaporated from the fabric due to drying (80% of the volatile components remain in the fabric).

[0115] The drying rate can be determined by applying the treatment solution composition to the fabric, measuring the change in mass over time after application to create a calibration curve, and using the mass of the fabric with the treatment solution composition applied after drying as the reference. For example, if the mass of the fabric with the treatment solution composition applied after drying time T2 is W T2 The mass of the fabric to which the treatment solution composition is attached after drying time T1 is W. T1 The mass W of the fabric to which the treatment solution composition is attached after a drying time t. t When this is the case, the drying rate at drying time t is {(W t -W T2 ) / (W T1 -W T2 It can also be calculated as )} × 100.

[0116] The drying rate can be appropriately set by controlling the drying temperature, drying time, and drying pressure. The drying temperature, drying time, and drying pressure may be referenced from those used in the drying process described above.

[0117] In the drying process, a drying rate of 50% to 90% allows organic solvents and water to easily adhere to the fabric, and the organic solvents tend to remain more uniformly near the fabric. As a result, the dye dissolves more effectively in the organic solvent near the fabric, improving its fixation to the fabric and resulting in prints with superior color development.

[0118] 5.3. Ink composition application process 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, after the processing liquid composition application step or drying step. 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.

[0119] 5.4. Washing Process 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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, a drying step of drying the processing liquid composition attached to the fabric after the processing liquid composition attachment step, 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 without being limited to the form of the fabric.

[0125] 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.

[0126] 6.2.2. Drying process For the drying process, please refer to the printing method described above.

[0127] 6.2.3.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.

[0128] 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 recording medium provided with the 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.

[0129] 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.

[0130] 6.2.4. 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.

[0131] 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.

[0132] 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 allows for the production of printed materials that have a better balance of wash fastness and texture, as well as superior color development and dry-cleaning resistance.

[0133] The heating temperature is preferably between 160°C and 220°C, and more preferably between 190°C and 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.

[0134] The heating time, depending on the heating temperature, is preferably between 30 and 120 seconds, and more preferably between 40 and 90 seconds. Heating within this range reduces the energy required for transfer, resulting in improved productivity of the printed material. Furthermore, it tends to improve the color development of the printed material.

[0135] 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 drying of the ink attached to the fabric is ensured, reducing the occurrence of blurring of the image.

[0136] 6.2.4. Other processes This method may include intermediate processing steps and post-processing steps as needed.

[0137] An intermediate processing step may include, for example, a step of preheating the fabric to which the processing liquid composition has been applied before the drying step. Post-processing steps include, for example, the process of cleaning the printed material.

[0138] 6.3. 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, and an ink composition application step, in which an ink composition is ejected from a recording head and applied 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.

[0139] 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.

[0140] 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.

[0141] In the ink composition application process, the maximum amount of ink applied to the fabric is 50 mg / cm². 2 More than 200mg / cm 2 Preferably, it is 80 mg / cm³ 2 More than 150mg / cm 2The following 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.

[0142] In this process, it is preferable to have a drying step after the treatment solution composition application step in which the treatment solution composition applied to the fabric is dried. Including this step tends to result in printed materials that have a better balance of wash fastness and texture, while also having superior color development and dry cleaning resistance. The drying step may also be described in the printing method described above.

[0143] 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.

[0144] For heating methods, refer to the methods used in the drying process of the above-described printing method.

[0145] During heating, it is preferable that the surface temperature of the heated fabric be between 60°C 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).

[0146] 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.

[0147] 6.2.3. Other processes This method may include intermediate and post-processing steps as needed. These steps can be described by referring to the other steps in the indirect printing recording method described above. [Examples]

[0148] The present invention will be described more specifically below using examples and comparative examples. The present invention is not limited in any way by the following examples.

[0149] 1. Preparation of dye printing treatment solution composition [Examples 1-16 and Comparative Examples 1-5] (Processing solutions 1-21) Each component was placed in a mixing tank to obtain the compositions shown in Tables 1 and 2, mixed and stirred, and then filtered through a 5 μm membrane filter to obtain treatment liquid compositions 1 to 21, respectively.

[0150] Note that the numerical values ​​for the amount of each component in Tables 1 and 2 represent mass percent. The amounts of resin particles and crosslinking agents are expressed as amounts (mass percent) calculated on a solid content basis. The "SP value" and "bp" for organic solvents represent the SP value obtained by Hansen and the standard boiling point (°C) at 1 atmosphere, respectively. Deionized water was used as the pure water, and it was added so that the mass of each treatment liquid composition was 100% by mass.

[0151] Furthermore, the components shown in Tables 1 and 2 are as follows: (Resin particles) • KT-8803… ELITER® KT-8803 (product name, Unitika Ltd., solid content: 30% by mass, glass transition temperature Tg: 65℃)

[0152] (Crosslinking agent) • #220… Fixer #220 (product name, Murayama Chemical Research Institute Co., Ltd., compound containing an isocyanate group having an isocyanurate skeleton in its structure, solid content: 40% by mass) • WS-500… Epocross (registered trademark) WS-500 (product name, manufactured by Nippon Shokubai Co., Ltd., compound containing an oxazoline group, solid content: 39% by mass)

[0153] (Organic solvents) Triethylene glycol (SP value: 13.5, standard boiling point: 287°C) • 2-pyrrolidone (SP value: 11.5, standard boiling point: 245°C) • Dipropylene glycol monomethyl ether (SP value: 10.1, standard boiling point: 188°C) • Dipropylene glycol dimethyl ether (SP value: 8.4, standard boiling point: 171°C) Triethylene glycol monobutyl ether (SP value: 10.0, standard boiling point: 278°C) • 1,2-Hexanediol (SP value: 12.1, standard boiling point: 170°C) Glycerin (SP value: 16.7, standard boiling point: 290°C) • Ethanol (SP value: 13.0, standard boiling point: 78℃)

[0154] [Table 1]

[0155] [Table 2]

[0156] 2. Preparation of inkjet ink composition [C Ink] Each component was placed in a mixing tank to achieve the composition shown in Table 3, 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 C. Note that the values ​​for each component in Table 3 represent mass percent.

[0157] Furthermore, the components shown in Table 3 are as follows:

[0158] (disperse dye) • Disperse Blue 359: CI Disperse Blue 359 (commercial product)

[0159] (Water-soluble organic solvent) Propylene glycol Glycerin Methyl triglycol

[0160] (Surfactants) • BYK(R)-348: BYK(registered trademark)-348 (product name, silicone-based surfactant, manufactured by BYK Chemie Japan Co., Ltd.)

[0161] [Table 3]

[0162] 3. Preparation of the printed material 3.1. Preparation of fabric to which the treatment solution composition is attached. (Examples 1-18, Comparative Examples 1-5, and Reference Examples 1 and 2) Each of the treatment liquid compositions 1 to 21 was used as the treatment liquid composition, and the treatment liquid composition was applied to the fabric. Specifically, the fabric to which the treatment liquid composition was applied was obtained in the following manner. As a fabric sample, a 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%. Subsequently, a heat press machine TP-608M (product name, manufactured by Taiyo Seiki Co., Ltd.) was used at a temperature of 200°C and a pressure of 4.2 N / cm². 3 The fabrics were dried for 3 to 40 seconds under the specified conditions to obtain fabrics coated with the treatment liquid compositions having the drying rates shown in Tables 4 and 5.

[0163] Here, the drying rate of the fabric to which the treatment liquid composition was attached after the drying process was calculated as follows. First, using treatment liquid 2 as the treatment liquid composition, under the same conditions as above, that is, the treatment liquid composition was immersed in white cotton braid #4000 (product name, manufactured by Toyobo Co., Ltd.), and the treatment liquid composition was applied to the fabric using a mangle roller to a wringing rate of 80%. Then, using a heat press machine TP-608M (product name, manufactured by Taiyo Seiki Co., Ltd.), at a temperature of 200°C and a pressure of 4.2 N / cm², 3 The fabric was dried under the conditions of 3 seconds. The mass W of the fabric to which the volatile components contained in the treatment solution 2 had adhered after drying was... B The mass W0 of the untreated fabric and the mass W of the fabric to which volatile components contained in the treatment solution 2 have adhered before drying.A The drying rate was measured and calculated using the above formula (1), and it was found to be 50%. The volatile components contained in the treatment solution 2 were triethylene glycol and water.

[0164] Similarly, using a fabric to which volatile components contained in the treatment solution composition obtained by drying for 40 seconds had adhered, the drying rate was calculated using formula (1) above, and the drying rate was 90%. In Examples 1 to 16 and Comparative Examples 1 to 5, drying was performed for an arbitrary time between 3 and 40 seconds, so the drying rate was between 50% and 90%.

[0165] Next, a calibration curve was created using the drying rate of 50% after a drying time of 3 seconds and the drying rate of 90% after a drying time of 40 seconds. In Examples 17 and 18, and Reference Examples 1 and 2, the drying rate was calculated from the drying time using this calibration curve.

[0166] Furthermore, the aperture ratio (S) was calculated using the following formula (2). S(%)=[(AB) / B]×100...(2) In formula (2), 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.

[0167] 3.2. Preparation of an intermediate recording medium to which the ink composition is attached. (Examples 1-18, Comparative Examples 1-5, and Reference Examples 1 and 2) C ink was filled into the cartridge of an inkjet printer PX-G930 (product name, manufactured by Seiko Epson Corporation). Then, on a coated surface of coated paper (TRANSJET Sportline 1254 (product name), manufactured by Chem Paper) used as an intermediate transfer medium, 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. 2 Under these conditions, the material was applied to form an image with a filled pattern. This resulted in obtaining an intermediate recording medium to which the ink composition was applied.

[0168] 3.3. Printing (Examples 1-18, Comparative Examples 1-5, and Reference Examples 1 and 2) The surface of the intermediate recording medium to which the image formed, to which the ink composition obtained above was attached, was then subjected to heat pressing using a heat press machine TP-608M (product name, manufactured by Taiyo Seiki Co., Ltd.) at a temperature of 200°C and a pressure of 4.2 N / cm² on each of the fabrics (cotton braids) to which the processing liquid composition obtained above was attached. 3 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.

[0169] 4. Evaluation of printed materials 4.1. Dry cleaning resistance For each of the prints obtained in Examples 1-18, Comparative Examples 1-5, and Reference Examples 1 and 2 through the aforementioned printing process, the dry-cleaning fastness was evaluated according to the ISO 105-D10 standard specified in JIS L0860's "Test Method for Color Fastness to Dry Cleaning" based on the following evaluation criteria. The results are shown in Tables 4 and 5. A rating of C or higher indicates that a good effect has been achieved. (Evaluation Criteria) A: Dry cleaning fastness exceeds level 4. B: Dry cleaning fastness is between grade 3-4 (intermediate grade) and grade 4. C: Dry cleaning fastness is between grade 2-3 (intermediate grade) and grade 3. D: Dry cleaning fastness is between grade 1-2 (intermediate grade) and grade 2. E: Dry cleaning fastness is grade 1 or lower.

[0170] 4.2. Color development The prints obtained in Examples 1-18, Comparative Examples 1-5, and Reference Examples 1 and 2, as described above, were left at room temperature of 25°C for 3 days. Subsequently, the color density (OD value) for C ink in each of the prints after standing was measured using a fluorescence spectrometer FD-7 (product name, manufactured by Konica Minolta, Inc.) under the following measurement conditions and at room temperature of 25°C. (Measurement conditions) • Observation light source: D65 • Observation field of view: 2° • Status: T • Polarizing filter: Not installed

[0171] Subsequently, the OD values ​​for the printed materials in Examples 1-18, Comparative Examples 1-5, and Reference Examples 1 and 2 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 4 and 5. A rating of C or higher indicates that a good effect has been obtained. (Evaluation Criteria) A: The OD value was 150% 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 125% or more but less than 150%. C: Compared to the OD value for the printed material in Comparative Example 2, the OD value was between 100% and 125%. D: Compared to the OD value for the printed material in Comparative Example 2, the OD value was 50% or more but less than 100%. E: The OD value was less than 50% compared to the OD value for the printed material in Comparative Example 2.

[0172] 4.3. Wash fastness For each of the prints obtained in Examples 1-18, Comparative Examples 1-5, and Reference Examples 1 and 2 from the aforementioned printing process, a wash fastness test was conducted in accordance with Method A-2 of JIS L0844 (Test Method for Color Fastness to Washing). Specifically, using a general household laundry detergent (fluorescent whitening agent-free), the prints from Examples 1-18, Comparative Examples 1-5, and Reference Examples 1 and 2 were washed in a household washing machine (ZABOON (product name), manufactured by Toshiba Corporation), rinsed, spun dry, and dried, and the discoloration of the prints was determined. The degree of discoloration was evaluated according to the following evaluation criteria, based on the discoloration grayscale of JIS L0804:2004 (ISO 105-C10(B2)). The results are shown in Tables 4 and 5. A rating of C or higher indicates that a good effect has been obtained. (Evaluation Criteria) A: The wash fastness is rated 5 or higher. B: Wash fastness is between level 4 and level 5. C: Wash fastness is between grade 3 and grade 4. D: Wash fastness is between grade 2 and grade 3. E: Wash fastness is less than level 2.

[0173] 4.4. Texture The texture of the printed materials obtained in Examples 1-18, Comparative Examples 1-5, and Reference Examples 1 and 2, as described above, was evaluated by sensory testing. Specifically, the judges evaluated the feel of the obtained printed materials according to the following criteria, and assessed their texture. The results are shown in Tables 4 and 5. Even those with an E rating were deemed suitable for practical use. (Evaluation Criteria) A: The printed material is soft and has a texture that is indistinguishable from the original feel of the fabric. B: The printed material is soft, but has a slightly rough texture. C: The printed material is somewhat hard and has a slightly rough texture. D: The printed material is hard and has a slightly rough texture. E: The printed material is hard and noticeably rough to the touch.

[0174] [Table 4]

[0175] [Table 5]

[0176] As shown in Tables 4 and 5, it was found that by applying the treatment solution composition of this embodiment to a fabric and then printing on the fabric to which the treatment solution composition has been applied, a printed product with excellent color development and dry cleaning resistance can be obtained.

[0177] From a comparison with Examples 2, 14, and 15, it was found that when the resin particle content is 1% by mass or more and 20% by mass on a solid content basis relative to the total amount of the treatment liquid composition, an imprinted product can be obtained that has better color development and dry cleaning resistance, as well as a better balance of wash fastness and texture.

[0178] A comparison of Example 2 and Example 16 revealed that using a compound containing an isocyanate group with an isocyanurate skeleton in its structure as a crosslinking agent resulted in a printed fabric with a better balance of wash fastness and texture, while also exhibiting superior color development and dry cleaning resistance.

[0179] From a comparison of Example 2 with Examples 1 and 3, it was found that when the organic solvent content is 10% by mass or more and 40% by mass or less relative to the total amount of the treatment solution composition, a printed fabric can be obtained that has an even better balance of wash fastness and texture, while also having even better color development and dry cleaning resistance.

[0180] From a comparison of Examples 17 and 18 with Reference Examples 1 and 2, it was found that when the drying rate of the fabric to which the treatment liquid composition adheres after the drying process is 50% to 90%, an imprinted product can be obtained that has an even better balance of wash fastness and texture, while also possessing even better color development and dry cleaning resistance.

Claims

1. A treatment liquid composition used by adhering it to a fabric, It contains resin particles, a crosslinking agent, an organic solvent, and water. The crosslinking agent includes a compound containing an isocyanate group, The isocyanate group-containing compound has an isocyanurate skeleton in its structure, The SP value of the aforementioned organic solvent is 13.5 or less. The standard boiling point of the aforementioned organic solvent is 100°C or higher. A dye printing treatment solution composition wherein the content of the organic solvent is 5% by mass or more relative to the total amount of the treatment solution composition.

2. The content of the organic solvent is 50% by mass or less relative to the total amount of the treatment liquid composition. The dye printing treatment solution composition according to claim 1.

3. The dye printing treatment liquid composition according to claim 1, wherein the organic solvent is one or more selected from the group consisting of glycols, glycol ethers, and nitrogen-containing solvents.

4. The dye printing treatment liquid composition according to claim 1, wherein the organic solvent comprises one or more selected from the group consisting of triethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, triethylene glycol monobutyl ether, and 2-pyrrolidone.

5. The dye printing treatment liquid composition according to claim 1, wherein the content of the resin particles is 1% by mass or more and 20% by mass or less in terms of solid content relative to the total amount of the treatment liquid composition.

6. The dye printing treatment liquid composition according to claim 1, wherein the amount of the crosslinking agent is 0.1% by mass or more and 5% by mass or less in terms of solid content relative to the total amount of the treatment liquid composition.

7. The dye printing treatment solution composition according to claim 1, wherein the fabric contains fibers having hydroxyl groups.

8. The dye printing treatment liquid composition according to claim 1, which is used to adhere to the fabric before dye printing on the fabric.

9. A dye printing treatment liquid composition according to any one of claims 1 to 8, and an inkjet ink composition, The inkjet ink composition comprises a disperse dye and water. Composition set.

10. A printing method comprising a step of applying a dye printing treatment solution composition according to any one of claims 1 to 8 to a piece of fabric.

11. A process of applying a dye printing treatment liquid composition provided in the composition set according to claim 9 to a piece of fabric, After the processing liquid composition application step, a drying step is performed to dry the processing liquid composition applied to the fabric, A dispensing step of dispensing the inkjet ink composition provided in the composition set according to claim 9 from a 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 treatment liquid composition after the drying step is attached, Inkjet printing method.

12. The printing method according to claim 11, wherein the drying rate of the fabric to which the dye printing treatment liquid composition is attached after the drying step is 50% or more and 90% or less, as represented by the following formula (1). Drying rate (%) = [1 - [(W)] Ｂ -W ０ ) / W Ａ 〕]×100・・・(1) (In formula (1), W Ｂ This indicates the mass of the fabric after drying, with the volatile components contained in the dye printing treatment solution composition attached to it. W ０ This indicates the mass of the untreated fabric. W Ａ This indicates the mass of the fabric before drying, to which the volatile components contained in the dye printing treatment solution composition have adhered.

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