Printing and dyeing method

Abstract

Provided is a printing and dyeing method whereby a variety of fabrics can be suitably printed and dyed, and a printed and dyed article having excellent color rendering properties and texture can be obtained. This textile printing method comprises: a pretreatment liquid attachment step for attaching a pretreatment liquid to a fabric; and a thermal transfer step for thermally transferring an image by causing a transfer medium, which forms the image by means of a sublimation transfer inkjet ink containing a disperse dye and water, to face the fabric to which the pretreatment liquid containing a polyester resin, a cross-linking agent, and water is adhered, thereby thermally transferring the image. The pretreatment liquid is adhered to the fabric in the pretreatment liquid adhesion step such that the product of the water absorbency [s] of the fabric as determined by the JIS L 1907: 2010 7.1. 3 sedimentation method and the amount [g / m2] of the polyester resin adhered to the fabric is 8.0 [s.g / m2] or more and 16.0 [s.g / m2] or less.

Description

Technical Field

[0001] The invention relates to a printing and dyeing method. Background Art

[0002] A dyeing method in which a sublimation dye is transferred to a natural fiber product by heating is used as a dyeing method for cloth, for example.

[0003] In order to efficiently apply transfer dyeing, a method of treating a natural fiber product with a pretreatment liquid before transferring a sublimation dye is studied.

[0004] More specifically, a method is proposed in which a hot-melt polyester resin having a glass transition temperature of 0°C or less is dissolved in a solvent selected from the group consisting of aromatic ethers and aromatic alcohols, the solution is dispersed in water, the obtained aqueous dispersion is attached to a natural fiber product, and after drying, a pattern surface of a transfer paper having a pattern represented by a sublimation dye is overlapped with the surface of the natural fiber product to which the resin is attached, and the pattern is transferred by heating (see Patent Document 1). Patent Document 1 states that the amount of polyester resin attached to the natural fiber product can be reduced to 1 to 5 g / m2 in terms of solid content. 2 Just left or right.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2002-235288 Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] However, in Patent Document 1, there is a problem that it is not possible to achieve both color development and texture depending on the type of fiber.

[0010] Technical solutions to solve problems

[0011] The present invention has been made to solve the above-mentioned technical problems, and can be implemented as the following application examples.

[0012] The printing and dyeing method according to the application example of the present invention comprises: a pre-treatment liquid attaching step of attaching the pre-treatment liquid to a cloth; and a thermal transfer step of placing a transfer medium having an image formed by a sublimation transfer inkjet ink containing a disperse dye and water opposite to the cloth to which the pre-treatment liquid is attached, so as to thermally transfer the image.

[0013] The pretreatment solution comprises a polyester resin, a cross-linking agent and water,

[0014] The water absorption of the fabric [s] obtained by the sedimentation method in JIS L 1907:2010 7.1.3 and the amount of the polyester resin attached to the fabric [g / m 2 ] is 8.0[s·g / m 2 ] and above and 16.0[s·g / m 2 ] The following method is used to adhere the pretreatment liquid to the fabric in the pretreatment liquid adhesion step. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is a table showing the components of the pretreatment liquids prepared in Preparation Examples A1 to A6 in summary.

[0016] Figure 2 is a table showing the composition of the sublimation transfer inkjet ink prepared by Preparation Example B1.

[0017] Figure 3 The types of pretreatment liquids, fabric conditions, and the amount of polyester resin attached to the fabric in Examples 1 to 16 are summarized as follows [g / m 2 ] and other tables.

[0018] Figure 4 The following table summarizes the types of pretreatment liquids, fabric conditions, and the amount of polyester resin attached to the fabric in Examples 17 to 22 and Comparative Examples 1 to 9 [g / m 2 ] and other tables. DETAILED DESCRIPTION

[0019] Hereinafter, preferred embodiments of the present invention will be described in detail.

[0020] [1] Printing and dyeing methods

[0021] First, the dyeing and printing method of the present invention will be described.

[0022] The dyeing and printing method of the present invention comprises: a pre-treatment liquid attaching step of attaching the pre-treatment liquid to a fabric; and a thermal transfer step of placing a transfer medium formed with an image by a sublimation transfer inkjet ink containing a disperse dye and water opposite to the fabric to which the pre-treatment liquid is attached, and thermally transferring the image. The pre-treatment liquid contains a polyester resin, a cross-linking agent, and water. In addition, the water absorption of the fabric [s] obtained by the sedimentation method of JIS L 1907:2010 7.1.3 and the amount of the polyester resin attached to the fabric [g / m 2 ] is 8.0[s·g / m 2 ] and above and 16.0[s·g / m 2] In the pretreatment liquid attachment step, the pretreatment liquid is attached to the fabric. It is considered that the smaller the value of the water absorption [s] of the fabric obtained by the sedimentation method of JIS L 1907:2010 7.1.3, the higher the water absorption.

[0023] With such a structure, various fabrics can be appropriately printed and dyed, and printed and dyed products with excellent color development and texture can be obtained.

[0024] On the other hand, when the above conditions are not met, satisfactory results cannot be obtained.

[0025] For example, if the pretreatment liquid attaching step is omitted and the disperse dye is directly transferred to the fabric that has not been pretreated with the pretreatment liquid, the color development of the obtained printed fabric may not be sufficiently excellent depending on the type of fabric.

[0026] In addition, if the pretreatment liquid does not contain a crosslinking agent, the color development of the resulting printed product cannot be sufficiently excellent. In addition, the durability of the printed product is poor.

[0027] If the product of the water absorbency of the fabric and the amount of the polyester resin attached to the fabric is less than the above lower limit, the color development of the obtained printed fabric cannot be sufficiently excellent.

[0028] On the other hand, when the product of the water absorbency of the fabric and the amount of the polyester resin attached to the fabric exceeds the above upper limit, the texture of the obtained printed fabric cannot be made sufficiently excellent.

[0029] In "JIS L 1907:2010 7.1.3 Sedimentation Method", the following apparatus and instruments are used. That is, as a water tank, a size that does not allow the test piece to touch is used, as a stopwatch, a stopwatch that can measure 0.5 seconds is used, and as water, water specified in A1 to A4 of Appendix 1 Table 1 (Classification and Quantity) of JIS K 0050 is used, and the temperature is 20°C ± 2°C.

[0030] In addition, in "JIS L 1907:2010 7.1.3 Sedimentation Method", the following operation is performed. That is, three test pieces of 10 mm × 10 mm in size are collected from the sample, and then the test pieces are placed with the measurement surface facing downward in a water tank filled with water, and then the time until the test pieces become wet and begin to settle in the water is measured with a stopwatch in units of 1 second. If the test piece does not settle even after 60 seconds or more, it is judged as not settling. However, if one of the three test pieces does not settle, an additional test piece is collected and the same test is performed. The test results are expressed by taking the average value of the time until the test piece becomes wet and begins to settle in the water as an integer for three of the three test pieces or four test pieces including the additional one that settle within 60 seconds according to Rule B of JIS Z 8401 (rounding method). However, if two or more of the three test pieces or the four test pieces including the additional one do not settle, the sample is judged to be non-sedimentary within 60 seconds. In addition, the front and back of the sample with obviously different front and back sides or the front and back of the sample with obviously different processing are tested separately, and the average values ​​of these are adopted as the water absorption value.

[0031] [1-1] Cloth

[0032] Fabrics are made by forming fibers into textiles, woven fabrics, non-woven fabrics, etc.

[0033] Examples of woven fabrics include plain weave, twill weave, satin weave, modified plain weave, modified twill weave, modified satin weave, fancy weave, jacquard weave, single weave, double weave, multiple weave, warp pile weave, weft pile weave, and leno weave.

[0034] The fabric can be processed into ready-made clothes or other apparel, etc. As ready-made clothes and other apparel, for example, sewn T-shirts, handkerchiefs, scarves, towels, handbags, cloth bags, curtains, bed sheets, window covers, furniture such as wallpaper, etc. can be cited.

[0035] The fabric can be processed into ready-made clothes or other apparel, etc. As ready-made clothes and other apparel, for example, sewn T-shirts, handkerchiefs, scarves, towels, handbags, cloth bags, curtains, bed sheets, window covers, furniture such as wallpaper, etc. can be cited.

[0036] The fibers constituting the cloth include, for example, natural fibers such as cotton, linen, wool, silk, leather, and wood; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, acrylic, and polyurethane; and biodegradable fibers such as polylactic acid. Blended fibers of two or more thereof may be used.

[0037] Among them, the fabric preferably includes fibers made of a material having a hydroxyl group.

[0038] Thus, the crosslinking agent contained in the pretreatment liquid can more firmly hold the polyester resin dyed with disperse dyes on the cloth by reacting with the hydroxyl group. As a result, the durability of the printed and dyed fabric, especially the washing durability and dry cleaning durability, can be made better. In addition, the feel and color development of the printed and dyed fabric can be made better. Examples of fibers composed of materials having hydroxyl groups include cellulose fibers such as cotton, rayon, and hemp.

[0039] The basis weight of the cloth is preferably, for example, 1.0 oz or more and 10.0 oz or less.

[0040] This makes it possible to better record on the cloth.

[0041] As the fabric, a fabric previously colored with a dye can be used. Since the pretreatment liquid used in the present invention is not easy to produce treatment marks, even the fabric previously colored can be used. That is, even if the fabric is colored, it is possible to perform printing and dyeing while suppressing the generation of treatment marks, so the quality or commercial value of the printed and dyed product as a product can be improved compared with the past.

[0042] As dyes for pre-coloring fabrics, for example, water-soluble dyes such as acid dyes and basic dyes, disperse dyes used in combination with dispersants, reactive dyes, solvent dyes, etc. In the case of using cotton fabrics as fabrics, disperse dyes and reactive dyes suitable for dyeing cotton are preferably used, and disperse dyes are more preferably used.

[0043] Depending on the difference in the above-mentioned conditions, the water absorption of the fabric, that is, the water absorption of the fabric [s] determined by the sedimentation method specified in JIS L 1907:2010 7.1.3, will differ.

[0044] [1-2] Pre-treatment liquid adhesion process

[0045] In the pretreatment liquid adhering step, a pretreatment liquid containing a polyester resin, a crosslinking agent, and water is made to adhere to the fabric.

[0046] In the pretreatment liquid attachment step, the water absorption of the fabric [s] obtained by the sedimentation method in JIS L 1907:2010 7.1.3 and the amount of the polyester resin attached to the fabric [g / m 2 ] is 8.0[s·g / m 2 ] and above and 16.0[s·g / m 2 ] The pretreatment liquid is attached to the fabric in the following manner.

[0047] As described above, in the present invention, the water absorption of the fabric [s] obtained by the sedimentation method in JIS L 1907:2010 7.1.3 and the amount of polyester resin attached to the fabric [g / m 2] is 8.0[s·g / m 2 ] and above and 16.0[s·g / m 2 ] In the following manner, the pretreatment liquid is attached to the fabric in the pretreatment liquid attachment step, but it is preferred that the water absorption of the fabric [s] is equal to the amount of the polyester resin attached to the fabric [g / m 2 ] satisfies the following conditions. That is, it is preferred that the water absorption of the fabric [s] and the amount of the polyester resin attached to the fabric [g / m 2 ] is 8.1[s·g / m 2 ] and above 15.8[s·g / m 2 ] or less, more preferably 8.1[s·g / m 2 ] and above and 14.0[s·g / m 2 ] or less, more preferably 8.1[s·g / m 2 ] and above 13.6[s·g / m 2 ]the following.

[0048] Thereby, the effects of the present invention described above are more significantly exhibited.

[0049] [1-2-1] Pretreatment solution

[0050] Next, the pretreatment liquid will be described in detail.

[0051] [1-2-1-1] Polyester

[0052] The pretreatment liquid contains a polyester resin.

[0053] Among various resins, the use of polyester resin can improve the durability of printed fabrics, especially the durability against washing and dry cleaning, etc. In addition, the feel and color development of printed fabrics can be improved.

[0054] The polyester resin is a resin having a structural unit derived from a polycarboxylic acid and a structural unit derived from a polyol.

[0055] As polycarboxylic acid, for example, terephthalic acid, isophthalic acid, phthalic acid, dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 2-sulfo terephthalate potassium, 5-sulfo isophthalate monosodium, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, succinic anhydride, p-hydroxybenzoic acid or salts thereof can be listed, and one or more selected from these can be used in combination. As salt, for example, potassium salt, sodium salt, calcium salt, magnesium salt, etc. can be listed.

[0056] Examples of the polyol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethyleneoxy glycol, dimethylolpropionic acid, glycerol, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolethylsulfonate, and potassium dimethylolpropionate. One or more selected from these may be used in combination.

[0057] The polyester resin preferably contains hydroxyl groups, carboxyl groups and sulfonic acid groups and sodium salts of these.

[0058] Examples of the sulfonic acid group-containing polyester resin include polyester resins having a structural unit derived from a polyvalent carboxylic acid, a structural unit derived from a polyol, and a structural unit derived from a sulfonic acid group-containing aromatic monomer.

[0059] Examples of the sulfonic acid group-containing aromatic monomer include 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfodicarboxylic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 4-sulfo-1,8-naphthalene dicarboxylic anhydride, or salts thereof, and one or more selected from these may be used in combination. Examples of the salt include potassium salt, sodium salt, calcium salt, magnesium salt, and the like, and sodium salt is preferred.

[0060] When the polyester resin contains the above-mentioned functional groups, the polyester resin can react with the crosslinking agent more appropriately, so that the adhesion to the cloth is improved. As a result, the durability of the printed fabric, especially the washing durability and dry cleaning durability, can be improved. In addition, the feel and color development of the printed fabric can also be improved. Such an effect is more significantly exerted when the crosslinking agent is a compound containing an isocyanate group or when the cloth contains fibers composed of a material having a hydroxyl group.

[0061] The polyester resin can be obtained by, for example, appropriately selecting one or more of the above-mentioned polycarboxylic acids, polyols, and, if necessary, sulfonic acid group-containing aromatic monomers and subjecting them to a polycondensation reaction by a conventional method.

[0062] As such a polyester resin, a commercial product may be used. Examples of commercial products include elitel (registered trademark) KA-5071S, KT-8803, KT-9204, KT-8701, KT-8904, KT-0507 (the above are trade names, manufactured by UNITIKA, polyester resin emulsion); Hytec (registered trademark) SN-2002 (trade name, manufactured by Toho Chemical Industry Co., Ltd., polyester resin emulsion); Plascoat (registered trademark) ) Z-221, Z-446, Z-561, Z-565, RZ-570, Z-592, Z-687, Z-690, Z-730, Z-760, RZ-105, RZ-570, RZ-760 (the above are trade names, manufactured by Huying Chemical Industry Co., Ltd.); Vylonal (registered trademark) MD-1200, MD-1500, MD-2000 (the above are trade names, manufactured by Toyobo Co., Ltd.).

[0063] The glass transition temperature of the polyester resin is preferably 25°C or higher, more preferably 35°C or higher and 90°C or lower, and further preferably 45°C or higher and 80°C or lower.

[0064] Thus, the molecular motion of the polyester resin in the use temperature range of the printed product obtained by the printing method of the present invention can be reduced, and the disperse dye can be more appropriately retained in the polyester resin. As a result, the color development of the printed product can be made more excellent, and fading over time can be more appropriately suppressed.

[0065] The polyester resin may be contained in the pretreatment liquid in any form, for example, in a dissolved state, but is preferably contained in a dispersed state without being in a particle form.

[0066] The content of the polyester resin in the pretreatment liquid is preferably 1.0 mass % to 20.0 mass %, more preferably 2.0 mass % to 15.0 mass %, and even more preferably 2.0 mass % to 10.0 mass %.

[0067] This makes it possible to more appropriately balance the durability, feel, and color development of the printed product.

[0068] [1-2-1-2] Cross-linking agent

[0069] The pretreatment solution contains a cross-linking agent.

[0070] This can impart crosslinking properties to the pretreatment liquid, and can appropriately bond the polyester resin, disperse dye, and fabric. As a result, a printed product having excellent color development and durability can be obtained.

[0071] As the crosslinking agent, it can be appropriately selected from known crosslinking agents for use, and the crosslinking reaction can be initiated at room temperature or by heat. As such a crosslinking agent, for example, a self-crosslinking crosslinking agent, a compound having a plurality of functional groups that react with an unsaturated carboxylic acid component in the molecule, a metal having a multivalent ligand, etc. can be cited, but it is preferably one or more selected from the group consisting of an isocyanate group-containing compound and an oxazoline group-containing compound, and more preferably an isocyanate group-containing compound.

[0072] This makes it possible to more appropriately balance the durability, feel, and color development of the printed product.

[0073] As the compound containing isocyanate group, for example, water-dispersible (blocked) polyisocyanate etc. can be listed. In addition, (blocked) polyisocyanate refers to polyisocyanate and / or blocked polyisocyanate. These compounds containing isocyanate group can be used alone or in combination of two or more.

[0074] Examples of water-dispersible polyisocyanates include polyisocyanates obtained by dispersing a polyisocyanate imparted with hydrophilicity by a polyethylene oxide chain in water using an anionic dispersant or a nonionic dispersant.

[0075] Examples of polyisocyanates include diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate; derivatives (modified products) of polyisocyanates such as trimethylolpropane adducts, biuret bodies, and isocyanurate bodies of these diisocyanates. In addition, the polyisocyanate may have an isocyanurate skeleton in its structure. These polyisocyanates may be used alone or in combination of two or more.

[0076] Water-dispersible blocked polyisocyanates are polyisocyanates formed by blocking the isocyanate groups of water-dispersible polyisocyanates using a blocking agent. Examples of the blocking agent 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 alone or in combination of two or more.

[0077] As the crosslinking agent, an isocyanate group-containing compound having an isocyanurate skeleton in the structure is preferred, and a water-dispersible polyisocyanate having an isocyanurate skeleton in the structure is more preferred. Since the isocyanate group-containing compound having an isocyanurate skeleton has at least three crosslinking points in the molecule, the adhesion between the polyester resin and the fabric can be made more appropriate. As a result, the durability, feel and color development of the printed product can be more appropriately balanced.

[0078] As such an isocyanate group-containing compound, commercially available products may be used, such as Fixer#100ECO, #104EA, #220, 70ECO, #70, #410, #400 (the above are trade names, manufactured by Murayama Chemical Research Institute Co., Ltd.); Elastron (registered trademark) BN-11, BN-27, BN-69, BN-77 (the above are trade names, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), etc.

[0079] Examples of the oxazoline group-containing compound include compounds having two or more oxazoline groups in the 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), 2,2'-octamethylene-bis(2-oxazoline), 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, oxazoline ring-containing polymers, etc., and one or more selected from these can be used in combination, but it is preferred to include a water-soluble oxazoline group-containing compound.

[0080] This makes it possible to more appropriately balance the durability, feel, and color development of the printed product.

[0081] Commercially available products may be used as such oxazoline group-containing compounds, such as Epocros (registered trademark) K-2010, K-2020, K-2030, K-2035E, WS-300, WS-500, and WS-700 (these are trade names, manufactured by Nippon Shokubai Co., Ltd.).

[0082] The cross-linking agent may be used alone or in combination of two or more.

[0083] The content of the cross-linking agent in the pretreatment liquid is preferably 0.1% by mass or more and 5.0% by mass or less, and more preferably 0.5% by mass or more and 3.0% by mass or less.

[0084] Thereby, when using various types of fabrics, the durability, feel, and color development of the printed product can be more appropriately balanced.

[0085] [1-2-1-3] Water

[0086] The pretreatment liquid contains water.

[0087] Water is mainly a component that imparts fluidity to the pretreatment liquid.

[0088] After the pretreatment liquid is attached to the fabric, most of the water evaporates and disperses.

[0089] Examples of water include pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and water from which ionic impurities are removed as much as possible, such as ultrapure water. In addition, water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is preferred because it can inhibit the generation of mold or bacteria when the pretreatment solution is stored for a long time.

[0090] The content of water in the pretreatment liquid is preferably 30.0 mass % or more and 98.0 mass % or less, more preferably 35.0 mass % or more and 96.0 mass % or less, and further preferably 40.0 mass % or more and 94.0 mass % or less.

[0091] This can suppress the increase in viscosity of the pretreatment liquid, making it possible to improve workability when attaching the pretreatment liquid to the fabric and drying properties after attachment. In addition, a higher affinity can be obtained for fabrics containing fibers having hydroxyl groups.

[0092] [1-2-1-4] Organic solvents

[0093] The pretreatment liquid may further contain an organic solvent.

[0094] This improves the permeability of the pretreatment liquid to the fabric, and makes the color development more excellent.

[0095] Examples of the organic solvent include glycerin, glycols, glycol ethers, nitrogen-containing solvents, esters, cyclic esters, monoalcohols, and the like. One or more selected from these may be used in combination, but preferably one or more selected from the group consisting of glycols, glycol ethers, and nitrogen-containing solvents.

[0096] This makes it possible to more appropriately balance the durability, feel, and color development of the printed product.

[0097] The boiling point of the organic solvent is preferably 100° C. or higher, more preferably 110° C. or higher and 300° C. or lower, and further preferably 120° C. or higher and 289° C. or lower.

[0098] This makes it possible to more appropriately balance the durability, feel, and color development of the printed product.

[0099] In addition, in this specification, unless otherwise specified, the boiling point means the boiling point at the standard atmospheric pressure of 1013.25 hPa, that is, the standard boiling point.

[0100] The SP value of the organic solvent is preferably 13.5 or less, more preferably 7.0 or more and 13.0 or less, and even more preferably 8.0 or more and 12.5 or less.

[0101] As a result, the compatibility of the organic solvent and the disperse dye contained in the sublimation transfer inkjet ink can be increased, and during the thermal transfer process, the disperse dye can be more appropriately dissolved in the organic solvent remaining near the fabric, and the polyester resin can be more appropriately dyed near the fabric. As a result, the durability, feel and color development of the printed product can be more appropriately balanced.

[0102] In addition, in this specification, SP value refers to the solubility parameter based on Hansen method, also known as Hansen SP value. Hansen method classifies SP value δ into 3 terms, expressed and calculated as δ2=δd2+δp2+δh2. Δd, δp, δh are solubility parameters corresponding to dispersion force term, dipole force term, and hydrogen bonding force term, respectively. The units of SP value and Hansen SP value are (cal / cm 3 ) 1 / 2 As the Hansen SP value, for example, a value derived by using Hansen-Solubility HSPiP as calculation software may be used.

[0103] Examples of the diol include ethylene glycol, triethylene glycol (SP value: 13.5, normal boiling point: 287° C.), 1,2-hexanediol (SP value: 12.1, normal boiling point: 170° C.), diethylene glycol (SP value: 12.1, normal boiling point: 245° C.), dipropylene glycol (SP value: 12.1, normal boiling point: 231° C.), 1,3-butanediol (SP value: 11.6, normal boiling point: 207° C.), 1,6-hexanediol (SP value: 12.3, normal boiling point: 250° C.), tetraethylene glycol (SP value: 12.3, normal boiling point: 314° C.), and 2-ethyl-1,3-hexanediol (SP value: 11.3, normal boiling point: 244° C.).

[0104] Examples of glycol ethers include dipropylene glycol monomethyl ether (SP value: 10.1, normal boiling point: 188° C.), dipropylene glycol dimethyl ether (SP value: 8.4, normal boiling point: 171° C.), triethylene glycol monobutyl ether (SP value: 10.0, normal boiling point: 278° C.), ethylene glycol diethyl ether (SP value: 8.3, normal boiling point: 189° C.), ethylene glycol monoethyl ether (SP value: 10.5, normal boiling point: 135° C.), ethylene glycol monophenyl ether (SP value: 11.5, normal boiling point: 245° C.), ethylene glycol monobutyl ether (SP value: 11.5, normal boiling point: 245° C.), and ethylene glycol monobutyl ether (SP value: 10.0, normal boiling point: 278° C.). P 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), propylene glycol monomethyl ether (SP value: 10.0, standard boiling point: 121°C), etc.

[0105] Examples of the nitrogen-containing solvent include 2-pyrrolidone (SP value: 11.5, normal boiling point: 245° C.), dimethylformamide (SP value: 12.2, normal boiling point: 153° C.), N-methyl-2-pyrrolidone (SP value: 11.2, normal boiling point: 202° C.), and aniline (SP value: 11.6, normal boiling point: 184° C.).

[0106] Examples of the esters include ethylene glycol diacetate (SP value: 10.0, normal boiling point: 190° C.), ethylene glycol monomethyl ether acetate (SP value: 9.2, normal boiling point: 145° C.), diethylene glycol monobutyl ether acetate (SP value: 8.5, normal boiling point: 246° C.), allyl acetate (SP value: 9.2, normal boiling point: 103° C.), and butyl acetate (SP value: 8.5, normal boiling point: 126° C.).

[0107] Examples of the cyclic esters include ε-caprolactone (SP value: 10.1, normal boiling point: 241° C.).

[0108] Examples of the monoalcohol include methanol, ethanol, 1-butanol (SP value: 11.3, normal boiling point: 118° C.), 2-ethyl-1-hexanol (SP value: 9.5, normal boiling point: 185° C.), and 3-butene-1-ol (SP value: 11.0, normal boiling point: 114° C.).

[0109] Among the above, it is preferred 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.

[0110] This makes it possible to more appropriately balance the durability, feel, and color development of the printed product.

[0111] The content of the organic solvent in the pretreatment liquid is preferably 5.0 mass % or more, more preferably 5.0 mass % or more and 70.0 mass % or less, further preferably 10.0 mass % or more and 55.0 mass % or less, and most preferably 15.0 mass % or more and 45.0 mass % or less.

[0112] This makes it possible to more appropriately balance the durability, feel, and color development of the printed product.

[0113] [1-2-1-5] Other ingredients

[0114] The pretreatment liquid may further contain components other than those described above. Hereinafter, such components are referred to as "other components" in this item.

[0115] Examples of other components include surfactants, solubilizers, viscosity adjusters, pH adjusters, antioxidants, preservatives, antifungal agents, anticorrosives, and chelating agents.

[0116] Examples of the preservative include sodium pentachlorophenol, sodium 2-thiopyridine-1-oxide, and 1,2-dibenzothiazoline-3-one.

[0117] As the preservative, a commercially available product may be used. Examples of the commercially available product include CRL, BND, GXL, XL-2, and TN (these are trade names) of the Proxel (registered trademark) series manufactured by Lonza Japan.

[0118] Among them, the content of other components in the pretreatment liquid is preferably 10.0 mass % or less, more preferably 7.0 mass % or less, and even more preferably 5.0 mass % or less.

[0119] [1-2-1-6] Other conditions

[0120] It is preferable that the pretreatment liquid satisfies the following conditions.

[0121] [1-2-1-6-1] Viscosity

[0122] The viscosity of the pretreatment liquid at 20° C. is preferably 1.5 mPa·s or more and 100 mPa·s or less.

[0123] This can further improve the coating properties such as the ease of diffusion of the pretreatment liquid when the pretreatment liquid is attached to the fabric.

[0124] The viscosity of the pretreatment liquid can be measured, for example, using a viscoelasticity tester MCR-300 (manufactured by Pysica Inc.) More specifically, the pretreatment liquid can be measured by adjusting the temperature to 20° C. and reading the shear viscosity [mPa·s] at a shear rate of 200 [1 / s].

[0125] [1-2-1-6-2] Surface tension

[0126] The surface tension of the pretreatment liquid at 25° C. is preferably 30 mN / m or more and 50 mN / m or less.

[0127] In this way, the wettability or permeability of the pretreatment liquid to the cloth can be made more appropriate. In addition, since the pretreatment liquid is easily and evenly absorbed by the cloth, the difference in the amount of adhesion generated when the pretreatment liquid is applied, that is, the generation of uneven coating, can be more effectively suppressed.

[0128] The surface tension of the pretreatment liquid can be measured, for example, using an automatic surface tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) More specifically, it can be measured by reading the surface tension when a platinum plate is wetted with the pretreatment liquid in an environment of 25°C.

[0129] [1-2-1-7] Method for preparing pretreatment solution

[0130] The pretreatment solution can be prepared by mixing the components in any order.

[0131] The mixture may be subjected to treatment such as filtration as necessary to remove impurities and foreign matter.

[0132] As a method for mixing the components, for example, a method of sequentially adding the components to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, stirring and mixing the components is used. As a filtering method, for example, centrifugal filtration, filter filtration, etc. can be cited.

[0133] [1-2-2] Attachment conditions

[0134] As a method for attaching the pretreatment liquid to the fabric, for example, there can be listed an immersion coating method in which the fabric is immersed in the pretreatment liquid, a roller coating method in which the pretreatment liquid is applied using a squeeze roller, a roller coater, etc., a spray coating method in which the pretreatment liquid is sprayed by a spray device, etc., an inkjet coating method in which the pretreatment liquid is sprayed by an inkjet method, and the like. One or more selected from these can be used in combination, but the roller coating method is preferred.

[0135] This can increase the degree of freedom in designing the amount of the pretreatment liquid that is attached, and can make it less likely that problems will occur during attachment, so that the pretreatment liquid can be more uniformly attached to the fabric.

[0136] The amount of the pretreatment solution deposited per unit area of ​​the fabric is preferably 0.02 g / cm 2 Above and 0.5g / cm 2 Below, more preferably 0.02 g / cm 2 Above and 0.3g / cm 2 the following.

[0137] This allows the pretreatment liquid to be more uniformly attached to the fabric, and can more effectively suppress uneven aggregation of images in the printed material, thereby improving color development properties.

[0138] [1-3] Thermal transfer process

[0139] In the thermal transfer step, a transfer medium on which an image is formed using a sublimation transfer inkjet ink containing a disperse dye and water is placed opposite to the fabric to which the pretreatment liquid is attached in the pretreatment liquid attaching step, and the image is thermally transferred.

[0140] Thus, the disperse dye is transferred to the fabric treated in the pre-treatment liquid attachment step, thereby obtaining a printed product.

[0141] In this step, the transfer medium on which the image is formed by the sublimation transfer inkjet ink and the cloth to which the pre-treatment liquid is attached are heated while being placed opposite to each other. In this step, it is more preferable to heat the transfer medium while the cloth to which the pre-treatment liquid is attached is in close contact with each other. Thus, for example, a clearer image can be recorded, i.e., dyed, on the cloth to which the pre-treatment liquid is attached.

[0142] Examples of the heating method include steam baking, hot pressing with dry heat, hot melt adhesive, HT steam engine with superheated steam, HP steam engine with pressurized steam, and the like, and dry heat is preferred.

[0143] This makes it possible to more appropriately balance the durability, feel, and color development of the printed product.

[0144] The heating temperature in this step is preferably 160°C or higher and 220°C or lower, and more preferably 190°C or higher and 210°C or lower.

[0145] This can further reduce the energy required for transfer, and can make the productivity of printed materials more excellent. In addition, it is possible to make the color development of printed materials more excellent.

[0146] The heating time also depends on the heating temperature, but is preferably 30 seconds to 120 seconds, more preferably 40 seconds to 90 seconds.

[0147] This can further reduce the energy required for transfer, and can make the productivity of printed materials more excellent. In addition, it is possible to make the color development of printed materials more excellent.

[0148] The amount of the sublimation transfer inkjet ink attached to the fabric by transfer is preferably 1.5 mg / cm per unit area of ​​the fabric. 2 Above and 6.0mg / cm 2 the following.

[0149] This improves the color development of the image transferred to the cloth, ensures the drying of the sublimation transfer inkjet ink attached to the cloth, and reduces the occurrence of image bleeding.

[0150] The transfer medium used in the thermal transfer process is formed by forming an image by sublimation transfer inkjet ink containing disperse dye and water.

[0151] The image is formed on the transfer medium by ejecting sublimation transfer inkjet ink onto the transfer medium using an inkjet method.

[0152] [1-3-1] Transfer media

[0153] As the transfer medium for forming an image by sublimation transfer inkjet ink, for example, paper such as ordinary paper, a recording medium provided with an ink receiving layer, etc. can be used. The above-mentioned recording medium provided with an ink receiving layer is, for example, called special paper for inkjet, coated paper, etc. Among them, it is preferred to provide a paper with an ink receiving layer containing inorganic particles such as silicon dioxide. Thus, a transfer medium as an intermediate recording material can be obtained that suppresses the generation of bleeding on the recording surface during the drying process of the sublimation transfer inkjet ink imparted to the transfer medium. In addition, if it is such a medium, it is easier to leave disperse dyes on the surface of the recording surface, and in the thermal transfer process, the sublimation of the disperse dyes can be carried out more efficiently.

[0154] [1-3-2] Sublimation transfer inkjet ink

[0155] Sublimation transfer inkjet inks used to form images on transfer media contain disperse dyes and water.

[0156] When forming an image on a transfer medium, a variety of sublimation transfer inkjet inks can be used.

[0157] This makes it possible to expand the expressible color gamut, for example.

[0158] [1-3-2-1] Disperse dyes

[0159] Sublimation transfer inkjet inks contain disperse dyes.

[0160] This makes it possible to obtain excellent color rendering properties for fabrics.

[0161] In sublimation transfer inkjet ink, disperse dyes are usually in the form of particles and dispersed in a dispersion medium. In addition, disperse dyes are usually nonionic dyes having a hydrophilic group and an appropriate polar group. Disperse dyes can be used alone or in combination of two or more.

[0162] Examples of the disperse dye 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.

[0163] More specifically, for example, CI Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 86; CI Disperse Red 11, 50, 53, 55, 55:1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190:1, 207, 239, 240; 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, 359; CI Disperse Orange 1, 1:1, 5, 20, 25, 25:1, 33, 56, 76; CI Disperse Violet 8, 17, 23, 27, 28, 29, 36, 57; CI Disperse Brown 2, etc.

[0164] In the present invention, since a printed product having a better dyeability and sufficient color development can be obtained with respect to the fabric to which the pretreatment liquid is attached, a cyan dye, a red dye, and a yellow dye are preferred. Since a printed product having a better dyeability and sufficient color development can be obtained with respect to the fabric, CI Disperse Blue 359 is more preferred as a cyan dye. CI Disperse Red 60 is more preferred as a red dye. CI Disperse Yellow 54 is more preferred as a yellow dye.

[0165] The content of the disperse dye in the sublimation transfer inkjet ink is preferably 0.05% by mass or more and 20% by mass or less.

[0166] [1-3-2-2] Water

[0167] Sublimation transfer inkjet inks contain water.

[0168] Water is mainly a component that imparts fluidity to the sublimation transfer inkjet ink.

[0169] After the sublimation transfer inkjet ink is attached to the transfer medium, most of the water evaporates and disperses.

[0170] Examples of water include pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and water from which ionic impurities are removed as much as possible, such as ultrapure water. In addition, water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is preferred because it can inhibit the growth of mold or bacteria when the sublimation transfer inkjet ink is stored for a long time.

[0171] The content of water in the sublimation transfer inkjet ink is preferably 30.0% by mass or more and 80.0% by mass or less.

[0172] [1-3-2-3] Dispersant

[0173] The sublimation transfer inkjet ink may further contain a dispersant.

[0174] This improves the dispersibility of the disperse dye, and makes it possible to further improve the storage stability of the sublimation transfer inkjet ink and the ejection stability of the inkjet method.

[0175] Examples of the dispersant include sodium naphthalenesulfonate formaldehyde condensate and resins.

[0176] The sodium naphthalenesulfonate formaldehyde condensate is a compound obtained by condensing a sulfonate having a naphthalene ring in the molecule with formaldehyde, or a salt thereof. The dispersant may be used alone or in combination of two or more.

[0177] When a resin serving as a dispersant is included, examples of the resin 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. One or more selected from these may be used in combination, but among them, urethane resins and styrene acrylic resins are preferred, and styrene acrylic resins are more preferred.

[0178] This further improves the dispersibility of the disperse dye, and makes the storage stability of the sublimation transfer inkjet ink and the ejection stability of the inkjet method more excellent.

[0179] The carbamate resin is not particularly limited as long as it is a resin having a carbamate bond in the molecule. Examples of the carbamate resin include polyether carbamate resins having an ether bond in the main chain in addition to the carbamate bond, polyester carbamate resins having an ester bond in the main chain, and polycarbonate carbamate resins having a carbonate bond in the main chain. The carbamate resin may be used alone or in combination of two or more.

[0180] As the urethane resin, commercial products may be used. Examples of commercial products include Takelac (registered trademark) W6110 (trade name) manufactured by Mitsui Chemicals, Acrytt (registered trademark) WBR-022U (trade name) manufactured by Daisei Fine Chemicals, Permarin (registered trademark) UX-368T (trade name), Uprene (registered trademark) UXA-307 (trade name), U-Coat (registered trademark) UWS-145 (trade name) manufactured by Sanyo Chemical Industries, Ltd., and Solsperse (registered trademark) 47000 (trade name) manufactured by Lubrizol.

[0181] Examples of the styrene acrylic resin include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylate copolymers, styrene-α-methylstyrene-acrylic acid copolymers, styrene-α-methylstyrene-acrylic acid-acrylate copolymers, etc. These copolymers may be in the form of, for example, random copolymers, block copolymers, alternating copolymers, and graft copolymers.

[0182] As the styrene acrylic resin, commercially available products may be used, such as Joncryl (registered trademark) 67 (trade name) manufactured by BASF Japan, and Solsperse (registered trademark) 43000 (trade name) manufactured by Lubrizol.

[0183] The content of the dispersant in the sublimation transfer inkjet ink is preferably 3.0% by mass or more and 8.0% by mass or less.

[0184] [1-3-2-4] Surfactants

[0185] The sublimation transfer inkjet ink may further contain a surfactant.

[0186] Examples of the surfactant include acetylene glycol surfactants, fluorine surfactants, silicone surfactants, etc. The surfactant may be used alone or in combination of two or more.

[0187] Examples of the acetylene glycol-based surfactant include 2,4,7,9-tetramethyl-5-decane-4,7-diol or an alkylene oxide adduct thereof, and 2,4-dimethyl-5-decane-4-ol or an alkylene oxide adduct thereof.

[0188] As the acetylene glycol surfactant, a commercially available product may be used, for example, Olfine (registered trademark) 104 series (trade name) or E series (trade name) manufactured by Nissin Chemical Industry Co., Ltd., Surfynol (registered trademark) series (trade name) manufactured by Air Products and Chemicals Incorporated, etc. may be cited.

[0189] Examples of the fluorinated surfactant include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkyl amine oxide compounds.

[0190] As the fluorine surfactant, a commercially available product may be used, and examples of the commercially available product include S-144 (trade name) and S-145 (trade name) manufactured by Asahi Glass Co., Ltd.

[0191] Examples of the silicone-based surfactant include polysiloxane-based compounds and polyether-modified silicone siloxanes.

[0192] As the silicone-based surfactant, commercially available products may be used, such as BYK (registered trademark) series 306, 307, 333, 341, 345, 346, 347, 348, 349 (these are trade names) manufactured by BYK Japan.

[0193] The content of the surfactant in the sublimation transfer inkjet ink is preferably 0.5% by mass or more and 5.0% by mass or less.

[0194] [1-3-2-5] Water-soluble organic solvents

[0195] The sublimation transfer inkjet ink may further include a water-soluble organic solvent.

[0196] Examples of the water-soluble organic solvent include glycerol; 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, Glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and triethylene glycol monomethyl ether; nitrogen-containing solvents such as 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, isobutanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol, etc.

[0197] The water-soluble organic solvent may be used alone or in combination of two or more.

[0198] Glycerin, glycols, and glycol monoethers can mainly function as penetrating solvents or humectants. Glycol monoethers tend to have strong properties as penetrating solvents, and glycerin and glycols tend to have strong properties as humectants.

[0199] The content of the water-soluble organic solvent in the sublimation transfer inkjet ink is preferably 5.0% by mass or more and 30.0% by mass or less.

[0200] [1-3-2-6] Other ingredients

[0201] The sublimation transfer inkjet ink may further contain components other than those described above. Hereinafter, such components are referred to as "other components" in this item.

[0202] Examples of other components include a solubilizing agent, a viscosity adjuster, a pH adjuster, an antioxidant, a preservative, a mildew preventer, an anticorrosive, and a chelating agent.

[0203] The content of other components in the sublimation transfer inkjet ink is preferably 10.0% by mass or less, more preferably 7.0% by mass or less, and even more preferably 5.0% by mass or less.

[0204] [1-3-3] Preparation method of sublimation transfer inkjet ink

[0205] The sublimation transfer inkjet ink can be prepared by mixing disperse dye, water, and other components as necessary in any order.

[0206] The mixture may be subjected to treatment such as filtration as necessary to remove impurities and foreign matter.

[0207] As a method for mixing the components, for example, a method of sequentially adding the components to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, stirring and mixing the components is used. As a filtering method, for example, centrifugal filtration, filter filtration, etc. can be cited.

[0208] [2] Printed and dyed materials

[0209] Next, the printed and dyed material according to the present invention will be described.

[0210] The printed and dyed product according to the present invention is produced using the above-mentioned printing and dyeing method of the present invention.

[0211] The printed and dyed products of the present invention have excellent color rendering and hand feel. In particular, in the printing and dyeing method of the present invention, various fabrics can be appropriately printed and dyed, so the printed and dyed products of the present invention can present the hand feel, texture, etc. of various fabrics while exhibiting excellent color rendering.

[0212] As mentioned above, although the preferred embodiment of the present invention was described, the present invention is not limited thereto.

[0213] For example, the dyeing and printing method of the present invention may further include other steps in addition to the pretreatment liquid attachment step and the thermal transfer step. Such steps include, for example, a pretreatment step performed on the fabric before the pretreatment liquid attachment step, an intermediate treatment step performed between the pretreatment liquid attachment step and the thermal transfer step, and a post-treatment step performed after the thermal transfer step.

[0214] Example

[0215] Next, specific examples of the present invention will be described. The present invention is not limited to the following examples.

[0216] [3] Preparation of pretreatment solution

[0217] (Preparation Example A1)

[0218] Each component was added to a mixture tank and mixed and stirred for 2 hours using a stirrer. Then, the mixture was filtered using a membrane filter with a pore size of 5 μm to obtain Figure 1 A pretreatment solution of the composition shown.

[0219] (Preparation Examples A2 to A6)

[0220] In addition to adjusting the types and amounts of ingredients used to Figure 1 A pretreatment liquid was prepared in the same manner as in Preparation Example A1 except for the components shown.

[0221] also, Figure 1 In the above, the numerical value of each component represents the content in the unit of mass %.

[0222] in addition, Figure 1 The components shown are as follows.

[0223] (Polyester resin)

[0224] ·KT-8803… Solid content of elitel (registered trademark) KT-8803 (trade name, manufactured by UNITIKA, solid content: 30% by mass, glass transition temperature Tg: 65°C)

[0225] ·KT-8701… Solid content of elitel (registered trademark) KT-8701 (trade name, manufactured by UNITIKA, solid content: 30% by weight, glass transition temperature Tg: 15°C)

[0226] (Cross-linking agent)

[0227] ·#220…fixer#220 (trade name, manufactured by Murayama Chemical Research Institute Co., Ltd., an isocyanate group-containing compound having an isocyanurate skeleton in its structure, solid content: 40% by mass)

[0228] ·K-2035E… Solid content of Epocros (registered trademark) K-2035E (trade name, manufactured by Nippon Shokubai Co., Ltd., oxazoline group-containing compound, solid content: 40% by mass)

[0229] [4] Preparation of sublimation transfer inkjet ink

[0230] (Preparation Example B1)

[0231] Each component was added to a mixture tank and mixed and stirred for 2 hours using a stirrer. Then, the mixture was filtered using a membrane filter with a pore size of 1 μm to obtain Figure 2 Sublimation transfer inkjet ink of the composition shown.

[0232] also, Figure 2 In the figures, the numerical values ​​of the components represent the content in the unit of mass %.

[0233] in addition, Figure 2 The components shown are as follows.

[0234] (Disperse dyes)

[0235] ·DB359: CI Disperse Blue 359 (commercially available)

[0236] (Surfactant)

[0237] BYK (R) -348: BYK (registered trademark) -348 (trade name, silicone surfactant, manufactured by BYK Japan)

[0238] [5]Manufacture of printed and dyed fabrics

[0239] (Example 1)

[0240] The pretreatment liquid prepared in Preparation Example A1 was used to obtain a fabric to which the pretreatment liquid was attached in the following manner. That is, the pretreatment liquid was impregnated into a cotton fabric having a water absorption of 0.9 [s], and the amount of polyester resin contained in the pretreatment liquid attached to the fabric was 10 [g / m 2], the pretreatment liquid was applied to the fabric using a squeeze roller. Then, a heat press TP-608M (trade name, manufactured by Taiyo Seiki Co., Ltd.) was used at a temperature of 200°C and a pressure of 4.2 N / cm 3 The cloth to which the pretreatment liquid was attached was obtained by drying it under the conditions of

[0241] On the other hand, using the sublimation transfer inkjet ink prepared in Preparation Example B1, a transfer medium having an image formed thereon by the sublimation transfer inkjet ink was obtained in the following manner. That is, the sublimation transfer inkjet ink was filled in the ink cartridge of the inkjet printer PX-G930 (trade name, manufactured by Seiko Epson). Thereafter, on the coated surface of coated paper (TRANSJET Sportline 1254 (trade name), manufactured by Chem Paper) as the transfer medium, the ink was injected at a resolution of 720 dpi × 720 dpi and an ink ejection amount of 12 mg / inch at a duty cycle of 100%. 2 The ink was adhered to the inkjet ink under the conditions of 100°C to form an image with a full pattern. Thus, a transfer medium having an image formed thereon by sublimation transfer inkjet ink was obtained.

[0242] The image-formed surface of the transfer medium obtained by forming an image and the cloth to which the pretreatment liquid was attached were placed opposite each other and superposed on each other, and a heat press machine TP-608M (trade name, manufactured by Taiyo Seiki Co., Ltd.) was used at a temperature of 200° C. and a pressure of 4.2 N / cm 3 Thermal transfer was performed under the conditions of 0.5 % and 1.5 % for 60 seconds to obtain a printed product.

[0243] (Examples 2 to 22)

[0244] In addition to the type of pretreatment solution, the condition of the fabric and the amount of polyester resin attached to the fabric [g / m 2 ]like Figure 3 , Figure 4 A printed material was produced in the same manner as in Example 1 except for the above-mentioned differences.

[0245] (Comparative Examples 1 to 9)

[0246] In addition to the type of pretreatment solution, the condition of the fabric and the amount of polyester resin attached to the fabric [g / m 2 ]like Figure 4 A printed material was produced in the same manner as in Example 1 except for the above-mentioned differences.

[0247] [6] Evaluation

[0248] The following evaluations were performed on the printed and woven materials according to the above-described examples and comparative examples.

[0249] [6-1] Color rendering

[0250] For the printed and dyed materials just after being manufactured involved in the above-mentioned embodiments and comparative examples, the OD value of the recording surface of the printed and dyed material, that is, the surface opposite to the transfer medium during the manufacture of the printed and dyed material, was measured using a spectrophotometer FD-7 (manufactured by Konica Minolta, Inc.) under the conditions of light source: D65 light source and viewing angle: 2 degrees, and evaluated according to the following criteria.

[0251] A: The OD value of the recording surface is 1.1 or more.

[0252] B: The OD value of the recording surface is 1.0 or more and less than 1.1.

[0253] C: The OD value of the recording surface is 0.9 or more and less than 1.0.

[0254] D: The OD value of the recording surface is 0.8 or more and less than 0.9.

[0255] E: The OD value of the recording surface is less than 0.8.

[0256] [6-2] Feel

[0257] The hand feeling of the printed and dyed products of each of the above-mentioned examples and comparative examples was evaluated by sensory tests. Specifically, the printed and dyed products were evaluated by any five judges as "not inferior to the original touch of the fabric" or "the printed and dyed product was hard and destroyed the original touch of the fabric", and the hand feeling was evaluated according to the results and the following evaluation criteria. When the evaluation result was B or above, the hand feeling was considered to be excellent.

[0258] A: Five judges answered that the texture was “not inferior to the original texture of the fabric.”

[0259] B: Four judges answered that the texture was “not inferior to the original texture of the fabric.”

[0260] C: Three judges answered that the texture was “not inferior to the original texture of the fabric.”

[0261] D: The number of judges who answered "It is as good as the original texture of the fabric" was 2 or 1.

[0262] E: No judges answered that the texture was “not inferior to the original texture of the fabric”.

[0263] [6-3] Fading over time

[0264] From the measurement of the OD value in the above-mentioned [6-1], irradiation with a D65 light source was further continued for 24 hours.

[0265] Thereafter, the OD values ​​of these printed materials were measured under the same conditions as those described in the above-mentioned [6-1].

[0266] Then, the measured OD value in the above [6-1] is set as OD0, and the measured OD value immediately after further continuous irradiation with light from a D65 light source for 24 hours from the measurement of the OD value in the above [6-1] is set as OD1. At this time, the fading rate [%] over time represented by {(OD1 / OD0)-1}×100 is calculated and evaluated according to the following criteria.

[0267] A: The fading rate over time is -1% or more.

[0268] B: The fading rate over time is -2% or more and less than -1%.

[0269] C: The fading rate over time is -4% or more and less than -2%.

[0270] D: The fading rate over time is -6% or more and less than -4%.

[0271] E: The fading rate over time is less than -6%.

[0272] These results are summarized together with the production conditions of the printed and dyed products involved in the above-mentioned embodiments and comparative examples. Figure 3 and Figure 4 Shown in.

[0273] In addition, Figure 3 , Figure 4 middle,

[0274] A cotton T-shirt fabric having a water absorption of 0.9 [s] is denoted as "F1",

[0275] A cotton T-shirt fabric having a water absorption of 1.3 [s] is designated as "F2".

[0276] A cotton dense woven plain cloth having a water absorption of 5.4 [s] is denoted as "F3".

[0277] As per Figure 3 , Figure 4 It can be seen that excellent results were obtained in the examples, whereas satisfactory results were not obtained in the comparative examples.

[0278] In addition, except for changing the content of the crosslinking agent in the pretreatment liquid in various ways within the range of 0.1 mass % to 5.0 mass %, printed materials were produced in the same manner as in the above-described examples and evaluated in the same manner as above. In this case, the same results as above were obtained.

Claims

1. A printing and dyeing method, characterized in that: have: a pre-treatment liquid attaching step of attaching the pre-treatment liquid to the fabric; and a thermal transfer step of placing a transfer medium on which an image is formed using a sublimation transfer inkjet ink containing disperse dye and water opposite to the fabric to which the pretreatment liquid is attached, to thermally transfer the image; The pretreatment solution comprises a polyester resin, a cross-linking agent and water, The product of the water absorption of the fabric determined by the sedimentation method in accordance with JIS L 1907:2010 7.1.3 and the amount of the polyester resin attached to the fabric was 8.0 s·g / m 2 Above and 16.0s·g / m 2 In the following embodiment, the pretreatment liquid is attached to the fabric in the pretreatment liquid attachment step, the unit of the water absorption is s, and the unit of the attachment amount is g / m 2 .

2. The printing and dyeing method according to claim 1, characterized in that: The polyester resin has a glass transition temperature of 25° C. or higher.

3. The printing and dyeing method according to claim 1 or 2, characterized in that: The cross-linking agent is a compound containing an isocyanate group.

4. The printing and dyeing method according to claim 1 or 2, characterized in that: The pretreatment liquid further comprises an organic solvent.

5. The printing and dyeing method according to claim 1 or 2, characterized in that: The fabric includes fibers composed of a material having a hydroxyl group.

6. The printing and dyeing method according to claim 1 or 2, characterized in that: The content of the polyester resin in the pretreatment liquid is 1.0 mass % or more and 20.0 mass % or less.

7. The printing and dyeing method according to claim 1 or 2, characterized in that: The content of the cross-linking agent in the pretreatment liquid is 0.1 mass % or more and 5.0 mass % or less.

Images