Dye printing treatment liquid composition, composition set, printing method, and ink-jet printing method

Abstract

To obtain a printed matter having excellent color development and a good feeling, through adhering a treatment liquid composition to fabric in advance and dye-printing onto the fabric with the treatment liquid composition adhered thereon.SOLUTION: A treatment liquid composition for dye-printing is to be used through adhering onto fabric, and includes a polyester resin and water. The polyester resin has a constitutional unit derived from an aromatic compound and a constitutional unit derived from a nonaromatic compound. The aromatic compound contains a phthalic acid. The nonaromatic compound contains a (poly)alkylene glycol. A content of the constitutional unit derived from the phthalic acid is 15 to 85 mol% with regard to 100 mol% of the polyester resin. A content of the constitutional unit derived from the (poly)alkylene glycol is 15 to 85 mol% with regard to 100 mol% of polyester resin.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a dye printing treatment liquid composition, a composition set, a printing method, and an ink-jet printing method. [Background technology]

[0002] Conventionally, when producing a printed textile by dyeing a fabric with a colorant, a technique of pretreating the fabric with a treatment liquid to improve the color development and fastness of the colorant has been known. For example, Patent Document 1 discloses a technique of applying a pretreatment liquid consisting of an aqueous composition to a polyester fabric. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-249773 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the pretreatment liquid of Patent Document 1 has the problem that it is difficult to obtain a printed item with excellent color development and good texture. In fact, Patent Document 1 is a technology for polyester fabrics and does not describe printing on natural fiber fabrics. Unlike natural fiber fabrics, polyester fabrics can be printed using dyes without using a pretreatment liquid. [Means for solving the problem]

[0005] The present invention provides a treatment liquid composition for dye printing that is to be applied to a fabric, the treatment liquid composition comprising a polyester resin and water, the polyester resin having structural units derived from an aromatic compound and structural units derived from a non-aromatic compound, the aromatic compound including phthalic acid, and the non-aromatic compound including a (poly)alkylene glycol, the content of the structural units derived from phthalic acid being 15 mol % or more and 85 mol % or less, relative to 100 mol % of the polyester resin, and the content of the structural units derived from (poly)alkylene glycol being 15 mol % or more and 85 mol % or less, relative to 100 mol % of the polyester resin. [Brief explanation of the drawings]

[0006] [Figure 1] 3 is a flowchart illustrating an example of an indirect textile printing method according to the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0007] Below, we will explain in detail the embodiment of the present invention (hereinafter referred to as the ``present embodiment''), but the present invention is not limited to this and various modifications are possible within the scope of the gist of the present invention.

[0008] 1. Dye printing treatment liquid composition The dye printing treatment liquid composition of this embodiment (hereinafter also referred to as "treatment liquid composition") is a treatment liquid composition to be applied to a fabric, and contains a polyester resin and water, the polyester resin having structural units derived from an aromatic compound and structural units derived from a non-aromatic compound, the aromatic compound including phthalic acid, and the non-aromatic compound including a (poly)alkylene glycol, the content of the structural units derived from phthalic acid being 15 mol % to 85 mol % based on 100 mol % of the polyester resin, and the content of the structural units derived from (poly)alkylene glycol being 15 mol % to 85 mol % based on 100 mol % of the polyester resin. The treatment liquid composition is preferably used to be applied to a fabric before dye printing.

[0009] According to this embodiment, the treatment liquid composition is applied to a fabric in advance, and then the fabric to which the treatment liquid composition has been applied is subjected to dye printing, thereby making it possible to obtain a printed fabric having excellent color development and good texture.

[0010] Although the reason why such excellent effects are obtained by this embodiment is not clear, the inventors presume as follows. That is, inks containing disperse dyes or the like typically used in textile printing have low affinity for fabrics containing fibers such as cotton, making dye printing difficult. On the other hand, inks containing disperse dyes or the like easily dye polyester resins, mainly due to non-covalent bonds such as π-π interactions and van der Waals forces with the aromatic compound-derived structural units in the polyester resin. Furthermore, polyester resins have high affinity for fabrics containing fibers, and therefore can be present on the fabric. Therefore, by attaching polyester resin to fabric using a treatment liquid composition, it is possible to impart the dyeability of inks containing disperse dyes or the like to fabrics containing fibers such as cotton.

[0011] However, since the aromatic compound-derived structural units in the polyester resin have a rigid structure, when a polyester resin having a high content of aromatic compound-derived structural units is used, the resulting printed textile tends to have poor texture. On the other hand, when a polyester resin having a low content of aromatic compound-derived structural units is used, the ink is less likely to dye the polyester resin, and the color development tends to be poor.

[0012] On the other hand, the treatment liquid composition of this embodiment contains a polyester resin having structural units derived from an aromatic compound and structural units derived from a non-aromatic compound, the aromatic compound including phthalic acid, the non-aromatic compound including (poly)alkylene glycol, and the content of the structural units derived from phthalic acid and the structural units derived from (poly)alkylene glycol are each specified. This polyester resin has appropriate flexibility due to the structural units derived from phthalic acid and the structural units derived from (poly)alkylene glycol, and also has excellent dyeability with ink due to the structural units derived mainly from phthalic acid, which is an aromatic compound. Therefore, it is believed that by applying this polyester resin to fabric, printed textiles with excellent color development and good texture can be obtained. However, the reasons are not limited to these.

[0013] Next, the components contained in the treatment liquid composition will be described, with the fabric being described later.

[0014] 1.1.Polyester resin The treatment liquid composition includes a polyester resin having structural units derived from an aromatic compound and structural units derived from a non-aromatic compound, the aromatic compound including phthalic acid, the non-aromatic compound including (poly)alkylene glycol, the phthalic acid-derived structural units and the (poly)alkylene glycol-derived structural units, the content of the phthalic acid-derived structural units being 15 mol % to 85 mol % relative to 100 mol % of the polyester resin, and the content of the (poly)alkylene glycol-derived structural units being 15 mol % to 85 mol % relative to 100 mol % of the polyester resin. When the treatment liquid composition contains such a polyester resin, it is possible to obtain a printed material having excellent color development and good texture.

[0015] In this specification, "structural units derived from phthalic acid" refers to structural units derived from the polymerization of phthalic acid in a polyester resin, as well as structural units formed by reactions that can give similar structural units. The same interpretation applies to "structural units derived from (poly)alkylene glycol."

[0016] The polyester resin contains a specific amount of structural units derived from phthalic acid as structural units derived from aromatic compounds. In this specification, phthalic acid includes orthophthalic acid, isophthalic acid, and terephthalic acid. The phthalic acid may have a substituent or may be a salt. Examples of the salt include potassium salt and sodium salt.

[0017] Since this tends to result in printed textiles with better color development and good texture, the content of structural units derived from phthalic acid is preferably 20 mol % or more and 80 mol % or less relative to 100 mol % of the polyester resin.

[0018] Examples of phthalic acids include alkylphthalic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, methyl orthophthalic acid, methyl isophthalic acid, and methyl terephthalic acid, hydroxyphthalic acids such as hydroxy orthophthalic acid, hydroxy isophthalic acid, and hydroxy terephthalic acid, aminophthalic acids such as amino orthophthalic acid, amino isophthalic acid, and amino terephthalic acid, nitrophthalic acids such as nitro orthophthalic acid, nitro isophthalic acid, and nitro terephthalic acid, sulfophthalic acids such as sulfo orthophthalic acid, sulfo isophthalic acid, and sulfoterephthalic acid, and salts thereof. Phthalic acids may be used alone or in combination of two or more.

[0019] Since there is a tendency to obtain printed textiles having better color development, better texture, and even better abrasion resistance and washing fastness, the phthalic acid is preferably at least one selected from the group consisting of orthophthalic acid, isophthalic acid, and terephthalic acid, and more preferably at least one selected from the group consisting of isophthalic acid and terephthalic acid.

[0020] Since a printed fabric tends to have better texture, abrasion resistance, and washing fastness as well as more excellent color development and color fastness, it is more preferable that the phthalic acid contains terephthalic acid and isophthalic acid. In this case, the molar ratio of the content of the structural units derived from isophthalic acid to the content of the structural units derived from terephthalic acid is preferably 0.5 or more and 3.0 or less. Since a printed fabric tends to have better texture, abrasion resistance, washing fastness, and color fastness as well as more excellent color development, it is more preferable that the molar ratio of the content of the structural units derived from isophthalic acid to the content of the structural units derived from terephthalic acid is 2.0 or more and 2.5 or less.

[0021] Although it is unclear why a printed textile having a molar ratio of the isophthalic acid-derived structural unit content to the terephthalic acid-derived structural unit content within the above range tends to have better texture, abrasion resistance, and washing fastness, as well as better color development and discoloration resistance, the inventors speculate as follows. That is, when the molar ratio is within the above range, the polymer chain in the polyester resin has a moderately bent structure. This makes it easier for ink containing a disperse dye or the like to be incorporated into the polymer chain, improving the dyeability of the polyester resin. Therefore, it is speculated that a printed textile having better texture, abrasion resistance, and washing fastness, as well as better color development and discoloration resistance, tends to be obtained. However, the reason is not limited to this.

[0022] The polyester resin contains a specific amount of (poly)alkylene glycol-derived structural units as structural units derived from a non-aromatic compound. In this specification, (poly)alkylene glycol is a non-aromatic compound, and the skeleton of the (poly)alkylene glycol has an alkylene group, but the skeleton may contain at least one bond selected from the group consisting of an ether bond and an ester bond. Furthermore, in this specification, (poly)alkylene glycol refers to both alkylene glycols having one alkylene group in their structure and polyalkylene glycols having two or more alkylene groups in their structure. The alkylene group may be linear, branched, or alicyclic.

[0023] Since this tends to result in printed textiles with better color development, color fastness, and texture, the content of the (poly)alkylene glycol-derived structural units is preferably 20 mol % or more and 80 mol % or less relative to 100 mol % of the polyester resin.

[0024] Since there is a tendency to obtain printed materials with better color development, color fastness, and better texture, the (poly)alkylene glycol is preferably a linear or branched (poly)alkylene glycol having 2 to 20 carbon atoms, and more preferably a linear or branched (poly)alkylene glycol having 2 to 10 carbon atoms.

[0025] Examples of alkyl glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1,2-propylene glycol, 1,3-propanediol, tripropylene glycol, tetrapropylene glycol, hexamethylene glycol, tetramethylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexa ... Examples of the (poly)alkylene glycol include dimethyl-1,3-pentanediol, diethyl-1,3-pentanediol, dipropyl-1,3-pentanediol, dibutyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, 1,3-adamantanediol, 2,2-adamantanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polytetramethylene oxide glycol. One type of (poly)alkylene glycol may be used alone, or two or more types may be used in combination.

[0026] Since this tends to result in printed textiles with even better color development, color fastness, and texture, the (poly)alkylene glycol is preferably at least one selected from the group consisting of ethylene glycol, neopentyl glycol, and diethylene glycol, and more preferably at least one selected from the group consisting of ethylene glycol and neopentyl glycol.

[0027] The polyester resin may contain, as constituent units, an aromatic compound other than phthalic acid and a non-aromatic compound other than (poly)alkylene glycol, as long as the effects of the present invention are achieved. Examples of such compounds include polycarboxylic acids such as 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic 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, and salts thereof; Examples of the polyvalent equol include p-xylylene glycol, bisphenol A-ethylene glycol adduct, dimethylolpropionic acid, dimethylolethylsulfonic acid, and salts thereof. Examples of the salt include potassium salt, sodium salt, calcium salt, and magnesium salt. These compounds may be used alone or in combination of two or more.

[0028] The polyester resin may contain one or more types of hydroxyl groups, carboxyl groups, sulfonic acid groups, or sodium salts thereof, as long as the effects of the present invention are achieved.

[0029] The sulfonic acid group-containing polyester resin has, for example, a constituent unit derived from phthalic acid, a constituent unit derived from a (poly)alkylene glycol, and a constituent unit 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 anhydride, as well as salts thereof. As for the salts, the above may be referred to, and sodium salts are preferred.

[0030] The polyester resin containing these groups can react well with the crosslinking agent described below, and has good adhesion to fabrics, preferably fabrics containing fibers having hydroxyl groups, making it possible to obtain printed textiles that have excellent color development and texture, as well as excellent abrasion resistance, washing fastness, and color fastness.

[0031] Since there is a tendency for a printed material having excellent color development, good texture, and better color fastness to be obtained, the polyester resin preferably has a glass transition temperature of 50° C. or higher. The lower limit is, for example, 180° C. or lower, and may be 150° C. or lower. In this specification, the glass transition temperature of the polyester resin can be measured, for example, by a differential scanning calorimeter (hereinafter also referred to as "DSC").

[0032] The polyester resin can be obtained by a conventional synthesis method. Examples of such methods include a method in which phthalic acid, (poly)alkylene glycol, and, if necessary, other compounds other than phthalic acid and (poly)alkylene glycol are simultaneously charged in desired amounts, and polymerized via an esterification reaction or transesterification reaction and a condensation reaction. The polymerization temperature is not particularly limited, but is preferably in the range of 180°C to 290°C. Polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide may be used for the polymerization. For specific synthesis methods, see the examples.

[0033] The polyester resin may be used alone or in combination of two or more kinds.

[0034] Since a printed textile having even better color development, texture, color fastness, abrasion resistance, and washing fastness tends to be obtained, the content of the polyester resin is preferably 0.05% by mass or more and 20% by mass or less, calculated as solids, relative to the total amount of the treatment liquid composition. Since a printed textile having even better color development, texture, abrasion resistance, color fastness, and washing fastness tends to be obtained, the content of the polyester resin is more preferably 2% by mass or more and 15% by mass or less, and even more preferably 3% by mass or more and 10% by mass or less, calculated as solids, relative to the total amount of the treatment liquid composition.

[0035] 1.2.Crosslinking Agent The treatment liquid composition preferably further contains a crosslinking agent. The inclusion of a crosslinking agent in the treatment liquid composition can impart crosslinking properties to the treatment liquid composition, making it possible to bond the polyester resin, the dye, and the fabric, which tends to result in printed items that have good texture, as well as excellent color development and abrasion resistance, and are also excellent in washing fastness and colorfastness.

[0036] The crosslinking agent can be appropriately selected from known crosslinking agents and may be one that initiates a crosslinking reaction at room temperature or by heat. Examples of such crosslinking agents include a crosslinking agent having self-crosslinking properties, a compound having multiple functional groups in the molecule that react with an unsaturated carboxylic acid component, and a metal having a polyvalent coordination site.

[0037] Since there is a tendency to obtain a printed product that has a good texture, yet has excellent color development, and is also excellent in abrasion resistance, washing fastness, and discoloration resistance, the crosslinking agent preferably contains an isocyanate group and / or an oxazoline group, and more preferably contains an isocyanate group.

[0038] Examples of isocyanate group-containing crosslinking agents include water-dispersible (blocked) polyisocyanates. The term "(blocked) polyisocyanates" refers to polyisocyanates and / or blocked polyisocyanates. These isocyanate group-containing crosslinking agents may be used alone or in combination of two or more.

[0039] Examples of water-dispersible polyisocyanates include those obtained by dispersing polyisocyanates, to which hydrophilicity has been imparted by polyethylene oxide chains, in water with an anionic dispersant or a nonionic dispersant.

[0040] Examples of polyisocyanates include diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate; and derivatives (modified products) of polyisocyanates such as trimethylolpropane adducts, biuret compounds, and isocyanurates of these diisocyanates. The polyisocyanate may have an isocyanurate skeleton in its structure. These polyisocyanates may be used alone or in combination of two or more.

[0041] The water-dispersible blocked polyisocyanate is obtained by blocking the isocyanate groups of the water-dispersible polyisocyanate with 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.

[0042] The crosslinking agent is preferably an isocyanate group-containing crosslinking agent having an isocyanurate skeleton in its structure, and more preferably a water-dispersible polyisocyanate having an isocyanurate skeleton in its structure. The isocyanate group-containing crosslinking agent having an isocyanurate skeleton has at least three crosslinking points, and therefore tends to be able to more favorably bond the polyester resin to the fabric. Therefore, it tends to produce printed products that have good texture, yet have even better color development and abrasion resistance, and are also excellent in washing fastness and discoloration resistance.

[0043] Commercially available isocyanate group-containing crosslinking agents include Fixer #100ECO, #104EA, #220, 70ECO, #70, #410, and #400 (all trade names, Murayama Chemical Laboratory Co., Ltd.) and Elastron (registered trademark) BN-11, BN-27, BN-69, and BN-77 (all trade names, Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0044] Examples of oxazoline group-containing crosslinking agents 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), Examples of the oxazoline ring-containing polymer 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 alone or in combination of two or more.

[0045] The oxazoline group-containing compound is preferably a water-soluble oxazoline group-containing compound, since it becomes possible to more firmly bind the polyester resin, the dye, and the fabric, and there is a tendency to obtain a printed product that has a good texture, more excellent color development, and is more excellent in abrasion resistance, washing fastness, and discoloration resistance.

[0046] Commercially available oxazoline group-containing crosslinking agents may also be used, such as EPOCROS (registered trademark) K-2010, K-2020, K-2030, K-2035E, WS-300, WS-500, and WS-700 (all trade names, manufactured by Nippon Shokubai Co., Ltd.).

[0047] The crosslinking agent may be used alone or in combination of two or more kinds.

[0048] Since there is a tendency to obtain a printed product that has a good texture, yet has excellent color development, and is also excellent in abrasion resistance, washing fastness, and discoloration resistance, the content of the crosslinking agent is preferably 0.1 to 10.0 mass % in terms of solid content with respect to the total amount of the treatment liquid composition.

[0049] 1.3.Water The treatment liquid composition contains water. After the treatment liquid composition is applied to the fabric, the water evaporates and dissipates upon drying. Examples of water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as water from which ionic impurities have been removed as much as possible, such as ultrapure water. Water sterilized by ultraviolet irradiation or the addition of hydrogen peroxide is preferred because it can suppress the growth of mold and bacteria when the treatment liquid composition is stored for a long period of time.

[0050] The water content is from 30 to 98% by mass, preferably from 35 to 96% by mass, and more preferably from 40 to 94% by mass, based on the total amount of the treatment liquid composition. By keeping the water content within this range, an increase in the viscosity of the treatment liquid can be suppressed, improving the workability when applying the treatment liquid to fabric and the drying properties after application. The treatment liquid composition is preferably an aqueous treatment liquid composition, since this provides higher affinity and safety to fabrics, preferably fabrics containing fibers having hydroxyl groups. In this embodiment, "aqueous" refers to a composition in which the water content is 30% by mass or more relative to the total amount of the composition.

[0051] 1.4.Other Ingredients The treatment liquid composition may contain various additives such as surfactants, dissolution aids, viscosity adjusters, pH adjusters, antioxidants, preservatives, mildew inhibitors, corrosion inhibitors, and chelating agents. The additives may be used alone or in combination of two or more.

[0052] The content of each additive 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.

[0053] 1.5. Method for preparing processing liquid composition The treatment liquid composition can be prepared by mixing the components in any order and, if necessary, performing filtration or the like to remove impurities, foreign matter, etc. The components can be mixed by sequentially adding the components to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, followed by stirring and mixing. Examples of filtration methods include centrifugal filtration and filter filtration.

[0054] 1.6. Physical properties of processing liquid composition The physical properties of the treatment liquid composition can be adjusted as desired depending on the type of fabric and the method of adhering the composition to the fabric, i.e., the application method, etc. The application method of the treatment liquid composition will be described later.

[0055] 1.6.1.Viscosity The viscosity of the treatment liquid composition at 20° C. is preferably 1.5 mPa·s or more and 100 mPa·s or less. By setting the viscosity of the treatment liquid within this range, it is possible to improve the coatability, such as the ease with which the treatment liquid spreads when applied to a fabric. The viscosity of the treatment liquid composition is measured, for example, using a viscoelasticity tester MCR-300 (Pysica). Specifically, the temperature of the treatment liquid composition is adjusted to 20°C, and the viscosity can be measured by reading the shear viscosity (mPa s) at a shear rate of 200 (1 / s).

[0056] 1.6.2.Surface tension The surface tension of the treatment liquid composition at 25°C is preferably 30 mN / m or more and 50 mN / m or less. By setting the surface tension of the treatment liquid composition at 25°C within this range, the treatment liquid composition exhibits appropriate wettability and permeability to the fabric. Furthermore, since the treatment liquid composition is more easily absorbed uniformly into the fabric, it is possible to suppress variations in the amount of adhesion that occur when the treatment liquid composition is applied, i.e., the occurrence of uneven application. The surface tension of the treatment liquid composition can be measured, for example, using an automatic surface tensiometer CBVP-Z (Kyowa Interface Science Co., Ltd.) Specifically, the surface tension can be measured by wetting a platinum plate with the treatment liquid composition in an environment of 25°C.

[0057] 2. Inkjet ink composition The inkjet ink composition (hereinafter also referred to as "ink composition") is used to produce a printed textile by printing on a fabric to which the treatment liquid composition of this embodiment has been applied. Next, the ink composition will be described. The ink composition according to this embodiment contains a disperse dye and water.

[0058] 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 liquid composition is applied. Disperse dyes are typically particulate colorants that are dispersed in a dispersion medium by a dispersant. Disperse dyes are typically nonionic dyes that have a hydrophilic group and a moderate polar group. Disperse dyes may be used alone or in combination of two or more.

[0059] Disperse dyes include, for example, 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.

[0060] Among these, sublimable dyes are preferred as dispersants. Here, the term "sublimable dye" refers to a dye that has the property of sublimating when heated. Specific examples of such sublimable 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, 20 7, 239, and 240; CI Vat 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.

[0061] In this embodiment, cyan dyes, red dyes, and yellow dyes are preferred because they provide better dyeability to the fabric to which the treatment liquid composition is applied, resulting in a printed product with sufficient color development. CI Disperse Blue 359 is more preferred as the cyan dye because they provide even better dyeability and a printed product 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.

[0062] In order to more effectively and reliably achieve the effects of this embodiment, the content of the coloring material is preferably 0.05% by mass or more and 20% by mass or less with respect to the total amount of the ink composition.

[0063] 2.2.Water The ink composition includes water. As for the water, reference can be made to the water contained in the above-mentioned treatment liquid composition, including the preferred embodiments.

[0064] In order to more effectively and reliably achieve the effects of this embodiment, the content of water is preferably 30% by mass or more and 80% by mass or less relative to the total amount of the ink composition.

[0065] 2.3.Dispersants The ink composition may include a dispersant. When an ink composition contains a dispersant, the dispersibility of the disperse dye is excellent and the clogging resistance of the ink composition is excellent. Examples of dispersants include sodium naphthalenesulfonate-formalin condensate and resin. Sodium naphthalenesulfonate-formalin condensate is a compound obtained by formalin condensation of a sulfonated compound having a naphthalene ring in the molecule, or a salt thereof. The dispersant may be used alone or in combination of two or more types.

[0066] The dispersant preferably contains a resin because it has better dispersibility. Examples of the resin include urethane-based resins, styrene-acrylic resins, acrylic resins, fluorene-based resins, polyolefin-based resins, rosin-modified resins, terpene-based resins, polyester-based resins, polyamide-based resins, epoxy-based resins, vinyl chloride-based resins, vinyl chloride-vinyl acetate copolymers, and ethylene-vinyl acetate-based resins. Among these, urethane-based resins and styrene-acrylic resins are preferred as the resin because of their excellent clogging resistance, and styrene-acrylic resins are more preferred.

[0067] The urethane resin is not particularly limited as long as it is a resin having a urethane bond in the molecule. Examples of the urethane resin include polyether-type urethane resins having an ether bond in the main chain in addition to the urethane bond, polyester-type urethane resins having an ester bond in the main chain, and polycarbonate-type urethane resins having a carbonate bond in the main chain. The urethane resins may be used alone or in combination of two or more.

[0068] As the urethane-based resin, commercially available products can also be used, such as Takelac (registered trademark) W6110 (trade name) manufactured by Mitsui Chemicals, Inc., Acrit (registered trademark) WBR-022U (trade name) manufactured by Taisei Fine Chemical Co., Ltd., Permarin (registered trademark) UX-368T (trade name), Euplen (registered trademark) UXA-307 (trade name), and U-Coat (registered trademark) UWS-145 (trade name) manufactured by Sanyo Chemical Industries, Ltd., and Solsverse (registered trademark) 47000 (trade name) manufactured by Lubrizol Corporation.

[0069] Examples of styrene-acrylic resins include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylate copolymers, styrene-α-methylstyrene-acrylic acid copolymers, and styrene-α-methylstyrene-acrylic acid-acrylate copolymers. These copolymers may be in the form of any of random copolymers, block copolymers, alternating copolymers, and graft copolymers.

[0070] As the styrene-acrylic resin, commercially available products can also be used, such as JONCRYL (registered trademark) 67 (product name) manufactured by BASF Japan Ltd. and SOLSVERSE (registered trademark) 43000 (product name) manufactured by Lubrizol Corporation.

[0071] In order to more effectively and reliably achieve the effects of this embodiment, the content of the dispersant is preferably 3.0% by mass or more and 8.0% by mass or less with respect to the total amount of the ink composition.

[0072] 2.4.Surfactants The ink composition may contain a surfactant. Examples of surfactants include acetylene glycol surfactants, fluorine surfactants, and silicone surfactants. The surfactants may be used alone or in combination of two or more.

[0073] Examples of acetylene glycol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and its alkylene oxide adduct, and 2,4-dimethyl-5-decyne-4-ol and its alkylene oxide adduct. Commercially available acetylene glycol surfactants can also be used, such as the Olfine (registered trademark) 104 series (trade name) and E series (trade name) manufactured by Nissin Chemical Industry Co., Ltd., and the Surfynol (registered trademark) series (trade name) manufactured by Air Products and Chemicals Inc.

[0074] Examples of fluorine-based surfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkyl amine oxide compounds. As the fluorine-based surfactant, commercially available products can also be used, such as S-144 (trade name) and S-145 (trade name) manufactured by Asahi Glass Co., Ltd.

[0075] Examples of silicone surfactants include polysiloxane compounds and polyether-modified organosiloxanes. As the silicone surfactant, commercially available products can also be used, such as BYK (registered trademark) series products 306, 307, 333, 341, 345, 346, 347, 348, and 349 (all trade names) manufactured by BYK Japan K.K.

[0076] In order to more effectively and reliably achieve the effects of this embodiment, the content of the surfactant is preferably 0.5% by mass or more and 5.0% by mass or less relative to the total amount of the ink composition.

[0077] 2.5. Water-soluble organic solvents The ink composition may contain a water-soluble organic solvent. Examples of the water-soluble organic solvent 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, and propylene glycol monomethyl ether. glycol monoethers such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and methyl triglycol; 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, isopropyl alcohol, n-butanol, 2-butanol, tert-butanol, iso-butanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol. The water-soluble organic solvents may be used alone or in combination of two or more.

[0078] In order to more effectively and reliably achieve the effects of this embodiment, 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.

[0079] 2.6.Other Ingredients The ink composition may contain various additives such as dissolution aids, viscosity adjusters, pH adjusters, antioxidants, preservatives, mildew inhibitors, corrosion inhibitors, and chelating agents for capturing metal ions that affect dispersion. The additives may be used alone or in combination of two or more.

[0080] Preservatives include sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, and 1,2-dibenzinethiazolin-3-one. Commercially available preservatives can also be used, such as CRL, BND, GXL, XL-2, and TN (all trade names) from the Proxel (registered trademark) series manufactured by Lonza Japan Co., Ltd. One type of preservative may be used alone, or two or more types may be used in combination.

[0081] The content of each additive is 0.01% by mass or more and 5.0% by mass or less relative to the total amount of the ink composition.

[0082] 2.7. Method for producing ink composition The ink composition can be prepared by mixing a disperse dye, water, and, if necessary, other components in any order, and removing impurities and foreign matter by filtration or the like as necessary. The components can be mixed by sequentially adding the components to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, followed by stirring and mixing. Examples of filtration methods include centrifugal filtration and filter filtration.

[0083] In order to disperse the disperse dye in the ink composition more effectively, a dye dispersant may be prepared in advance and used in place of the disperse dye when preparing the ink composition. The dye dispersant can be obtained, for example, by mixing the disperse dye, water, and dispersant in any order and dispersing the mixture using a paint shaker or the like.

[0084] 3. Composition Set The composition set includes the treatment liquid composition and the ink composition.

[0085] In this embodiment, the treatment liquid composition is applied to a fabric in advance to obtain a fabric to which the treatment liquid composition is applied. Then, the fabric to which the treatment liquid composition is applied is printed using an ink composition, thereby obtaining a printed textile having excellent color development and a good texture.

[0086] 4.Fabric Examples of the fabric according to the present 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. The fabric may also be a blend of these fibers.

[0087] The fabric preferably contains a fiber having a hydroxyl group, more preferably cotton, because this results in a printed product with better color development and better texture. The fiber having a hydroxyl group may also be a blend of these fibers.

[0088] Examples of the form of the fabric include woven fabrics, knitted fabrics, nonwoven fabrics, fabrics, as well as clothing and other accessories. Examples of clothing and other accessories include furniture such as sewn T-shirts, handkerchiefs, scarves, towels, carrier bags, cloth bags, curtains, sheets, bedspreads, and wallpaper; and fabrics before and after cutting as parts before sewing. These forms include long rolls, cut to a specified size, and finished products. The fabric may be any fabric as long as the treatment liquid composition is adhered to it, and fabrics to which the treatment liquid composition has been applied in advance may also be used.

[0089] The basis weight of the fabric is preferably, for example, 1.0 oz or more and 10.0 oz or less. If the basis weight of the fabric is in this range, good recording can be performed.

[0090] The fabric may be one that has been colored in advance with a dye. The treatment liquid composition is less likely to leave treatment marks, so it can be used even on pre-colored fabrics. In other words, even if the fabric is colored, it is possible to perform textile printing with reduced treatment marks, and this makes it possible to improve the quality and commercial value of the printed textile product compared to conventional methods.

[0091] Examples of dyes that can be used to pre-color a fabric include water-soluble dyes such as acid dyes and basic dyes, disperse dyes that are used in combination with dispersants, reactive dyes, solvent dyes, etc. When a cotton fabric is used as the fabric, it is preferable to use a disperse dye or reactive dye that is suitable for dyeing cotton, and a disperse dye is more preferable.

[0092] 5. Printing method The textile printing method of the present embodiment includes a treatment liquid composition applying step of applying the treatment liquid composition to a fabric. This step provides a fabric having the treatment liquid composition adhered thereto. Furthermore, by adhering an ink composition to this fabric, a printed textile having excellent color development and good texture can be obtained.

[0093] The textile printing method preferably includes, after the treatment liquid composition application step, an ink composition application step in which an ink composition is applied to the fabric to which the treatment liquid composition has been applied. The ink composition 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, with regard to the ink composition application step, reference can be made to the textile printing method using the inkjet method described below. The printing method can be applied to various fabrics and can produce good printing.

[0094] The amount of the treatment liquid composition applied to the fabric is, for example, 0.02 g / cm 2 More than 0.5g / cm 2 It is preferable to apply it so that the density is 0.02 g / cm or less. 2 More than 0.3g / cm 2 By setting the amount of treatment liquid composition to be applied within the above range, the treatment liquid composition can be applied more uniformly to the fabric, aggregation unevenness of the image on the printed textile can be further suppressed, and color development can be improved.

[0095] Examples of methods for applying the treatment liquid composition to a fabric include a dip 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, a roll coater, or the like, a spray coating method in which the treatment liquid composition is sprayed using a spray device, or an inkjet coating method in which the treatment liquid composition is sprayed by an inkjet method. Of these coating methods, the treatment liquid composition may be applied to the fabric using one method alone, or two or more methods may be combined to apply the treatment liquid composition to the fabric. In this embodiment, it is preferable to apply the treatment liquid composition to the fabric using a roller such as a mangle roller or a roll coater, because this increases the degree of freedom in designing the amount of treatment liquid composition to be applied, makes it less likely that problems will occur during application, and enables the treatment liquid composition to be applied uniformly to the fabric.

[0096] The textile printing method preferably includes a treatment liquid composition drying step of drying the treatment liquid composition applied to the fabric after the treatment liquid composition application step of applying the treatment liquid composition to the fabric. The treatment liquid composition may be dried by natural drying, but is preferably dried with heating, since this increases the amount of treatment liquid composition applied to the fabric and also increases the drying speed.

[0097] The drying temperature is preferably, for example, 180°C or lower. This prevents the dye from sublimating due to heat drying, even if the fabric is pre-colored with a dye, and prevents the fabric color from fading. The lower limit of the heating temperature is sufficient as long as the medium, such as water, contained in the treatment liquid composition is volatilized, and is preferably, for example, 100°C or higher.

[0098] Examples of heating methods include heat pressing, atmospheric steam, high-pressure steam, and Thermofix, and examples of heat sources include infrared rays (lamp).

[0099] In the textile printing method, after the treatment liquid composition is applied to the fabric, a washing step may be included as necessary. By including this step in the textile printing method, components contained in the treatment liquid composition that are not applied to the fabric can be removed.

[0100] 6. Inkjet printing method The inkjet textile printing method is a method in which an ink composition is applied to a fabric to which a treatment liquid composition has been applied using an inkjet method. By employing the inkjet method, dyed portions of fine patterns can be easily and reliably formed. Furthermore, the method can be applied to various fabrics, and good printing can be achieved. The inkjet textile printing method can also be used to achieve good printing with little color difference between the front and back of thick fabrics. Examples of inkjet textile printing methods include an indirect textile printing method and a direct textile printing method.

[0101] 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 containing an ink composition and a recording head connected thereto, and is capable of ejecting the ink composition from the recording head to form an image on a fabric to which the treatment liquid composition has been applied, or on transfer paper as an intermediate transfer medium. Furthermore, either a serial type or a line type inkjet recording device 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 intermittently and in a predetermined volume from the nozzle holes of the recording head at a predetermined timing. This allows the ink composition to be applied to the fabric or transfer paper, forming a predetermined transfer image.

[0102] Generally, in a serial inkjet recording device, the direction of transport of the recording medium and the direction of reciprocating motion of the recording head intersect, and the relative positional relationship between the recording medium and the recording head is changed by combining the reciprocating motion of the recording head and the transport motion of the recording medium. In this case, the recording head generally has a plurality of nozzle holes arranged therein, and a row of the nozzle holes, i.e., a nozzle row, is formed along the direction of transport of the recording medium. In addition, the recording head may have a plurality of nozzle rows formed therein depending on the type and number of ink compositions.

[0103] Generally, in a line-type inkjet recording device, the recording head does not reciprocate, but changes the relative positional relationship between the recording medium and the recording head by conveying the recording medium. Even in this case, the recording head generally has a plurality of nozzle holes arranged therein, and a nozzle row is formed along a direction intersecting the conveying direction of the recording medium.

[0104] 6.2. Indirect printing recording method The inkjet printing method of this embodiment includes a treatment liquid composition application step in which a treatment liquid composition is applied to a fabric; a discharge step in which an ink composition is ejected from a recording head and applied to an intermediate transfer medium; and a transfer step in which the ink composition applied to the intermediate transfer medium is transferred to the fabric to which the treatment liquid composition obtained in the treatment liquid composition application step has been applied. Specifically, in this printing method, an ink composition containing a disperse dye such as a sublimation dye is ejected from a liquid ejection head, which is a recording head, and applied to the intermediate transfer medium. The surface of the intermediate transfer medium to which the ink composition has been applied and the surface of the fabric to which the treatment liquid composition has been applied are then heated while facing each other, thereby transferring the disperse dye contained in the ink composition to the fabric to which the treatment liquid composition has been applied. In this embodiment, this type of printing method is also referred to as an indirect printing recording method. This printing method allows for good printing regardless of the type of fabric.

[0105] 6.2.1. Treatment composition application step For the treatment liquid composition application step, the above-mentioned textile printing method can be referred to.

[0106] 6.2.2.Discharge process In the ejection step, the heated ink composition is ejected from the liquid ejection head and adhered to the intermediate transfer medium. Specifically, the pressure generating means is driven to eject the ink composition filled in the pressure generating chamber of the liquid ejection head from the nozzle.

[0107] Examples of intermediate transfer media that can be used include paper such as plain paper and recording media provided with an ink-receiving layer. Recording media provided with the ink-receiving layer are referred to as, for example, inkjet paper and coated paper. Among these, paper provided with an ink-receiving layer containing inorganic particles such as silica is more preferred. This makes it possible to obtain an intermediate recording material 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, such a medium makes it easier to retain the disperse dye on the surface of the recording surface, allowing for more efficient sublimation of the disperse dye in the subsequent transfer process.

[0108] In this step, multiple ink compositions may be used. This makes it possible to, for example, broaden the color gamut that can be expressed. One of the multiple ink compositions may be the ink composition of this embodiment, or two or more of the multiple ink compositions may be the ink composition of this embodiment.

[0109] 6.2.3. Transfer process The transfer step is a step in which the surface of the intermediate transfer medium on which the ink composition is adhered and the surface of the fabric on which the treatment liquid composition is adhered are heated while facing each other, thereby transferring the disperse dye contained in the ink composition to the fabric on which the treatment liquid composition is adhered. As a result, the disperse dye is transferred, and a printed textile is obtained, which is the fabric on which the ink composition is adhered.

[0110] In this step, the intermediate transfer medium to which the ink composition has been applied may be heated while facing the fabric to which the treatment liquid composition has been adhered. In this step, it is more preferable to heat the intermediate transfer medium and the fabric to which the treatment liquid composition has been adhered while they are in close contact with each other. This makes it possible, for example, to record a clearer image on the fabric to which the treatment liquid composition has been adhered, i.e., to dye it.

[0111] 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 subjected to heat treatment immediately or after a predetermined time has elapsed. Dry heat is preferred as a heating method, as it provides a printed fabric with excellent texture as well as excellent friction fastness, washing fastness, and color development.

[0112] The heating temperature is preferably 160° C. or higher and 220° C. or lower, and more preferably 190° C. or higher and 210° C. or lower. When the heating temperature is within the above range, the energy required for transfer can be reduced, which tends to improve the productivity of the printed textile. In addition, the color development of the printed textile tends to be improved.

[0113] The heating time, although depending on the heating temperature, is preferably 30 seconds or more and 120 seconds or less, more preferably 40 seconds or more and 90 seconds or less. By keeping the heating time within the above range, the energy required for transfer can be reduced, and the productivity of the printed textile tends to be better. In addition, the color development of the printed textile tends to be better.

[0114] The amount of the ink composition that adheres to the fabric by transfer is, for example, 1.5 mg / cm 2 per unit area of ​​the fabric. 2 More than 6.0mg / cm 2 When the amount of the ink composition applied is within the above range, the color development of the image formed by textile printing is improved, and the drying property of the ink applied to the fabric is ensured, thereby reducing the occurrence of bleeding of the image.

[0115] 6.2.4. Other processes The method may include intermediate and post-processing steps as required.

[0116] An example of the intermediate treatment step is a step of preheating the fabric to which the treatment liquid composition has been applied. An example of the post-treatment step is a step of washing the printed material.

[0117] 6.2. Direct printing recording method The inkjet textile printing method may include a treatment liquid composition application step of applying a treatment liquid composition to a fabric, and an ink composition application step of ejecting an ink composition from a recording head to apply the ink composition to the fabric to which the treatment liquid composition obtained in the treatment liquid composition application step has been applied. In this embodiment, such a textile printing method is also referred to as a direct textile printing recording method. This textile printing method can easily and reliably form dyed portions with fine patterns. Furthermore, because it does not require the use of a plate such as an intermediate transfer medium, it has excellent on-demand properties and can be suitably adapted to small-scale production and multi-item production.

[0118] 6.2.1. Step of Obtaining Fabric with Treatment Liquid Composition Adhered For the treatment liquid composition application step, the above-mentioned textile printing method can be referred to.

[0119] 6.2.2. Ink composition application step In the ink composition application step, an ink composition is applied to the fabric to which the treatment liquid composition has been applied. The ink composition application step may also include a step of applying a further ink composition onto the area to which the ink composition has been applied.

[0120] In the ink composition application process, the maximum amount of ink applied to the fabric is 50 mg / cm 2 More than 200mg / cm 2 Preferably, it is 80 mg / cm or less. 2 More than 150mg / cm 2When the maximum adhesion amount is within the above range, the color development is better. In addition, the image has excellent resistance to rubbing, and aggregation unevenness tends to be less noticeable.

[0121] In this step, it is preferable to heat the fabric to which the treatment liquid composition has been applied when the ink composition is applied, which makes it possible, for example, to record a clearer image on the fabric to which the treatment liquid composition has been applied, i.e., to dye the fabric.

[0122] Examples of the heating method include a heat press method, a normal pressure steam method, a high pressure steam method, and a Thermofix method. Examples of the heat source for heating include hot air, infrared rays, and microwaves.

[0123] During heating, the surface temperature of the heated fabric is preferably 60°C or higher and 180°C or lower. Having a surface temperature within this range reduces damage to the inkjet head and fabric, and also makes it easier for the ink to wet and spread evenly across the fabric and penetrate more easily. The surface temperature can be measured, for example, using a non-contact thermometer (product name "IT2-80", manufactured by Keyence Corporation).

[0124] The heating time is preferably, for example, from 5 seconds to 5 minutes. By keeping the heating time within this range, it becomes possible to sufficiently heat the fabric while reducing damage to the inkjet head and the fabric.

[0125] 6.2.3. Other processes This method may include intermediate and post-treatment steps as needed, and for these steps, reference can be made to the other steps in the indirect textile printing and recording method described above. [Example]

[0126] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples.

[0127] 1. Synthesis of polyester resin [Polyester resins A to I] First, a mixture containing phthalic acid and (poly)alkylene glycol was prepared so as to have the composition shown in Table 1. This mixture was placed in an autoclave and heated at 220°C for 4 hours to carry out an esterification reaction. Next, tetrabutyl titanate was added to the autoclave as a catalyst, and the temperature was raised to 230°C, and the pressure was gradually reduced to 13 Pa after 1.5 hours. The polycondensation reaction was continued under these conditions, and after 4 hours, the pressure inside the autoclave was returned to normal pressure with nitrogen gas and cooled to room temperature, thereby synthesizing polyester resins A to I.

[0128] The numerical values ​​for the blending amount of each component in Table 1 represent mol %. "Tg" for polyester resin represents the glass transition temperature (°C). "Isophthalic acid / terephthalic acid" represents the molar ratio of the content of structural units of isophthalic acid to the content of structural units derived from terephthalic acid in the polyester resin.

[0129] [Table 1]

[0130] 2. Preparation of dye printing treatment liquid composition [Examples 1 to 11 and Comparative Examples 1 to 5] Each treatment liquid composition was obtained by placing the components in a mixing tank, mixing and stirring, and filtering through a 5 μm membrane filter so as to obtain the compositions shown in Tables 2 and 3. In Comparative Example 1, no treatment liquid composition was prepared. The numerical values ​​for the blending amount of each component in Tables 2 and 3 represent mass %. The blending amount of the crosslinking agent represents the blending amount (mass %) calculated as solid content.

[0131] The components shown in Tables 2 and 3 are as follows: (polyester resin) A to I: Polyester resins A to I obtained by the above synthesis

[0132] (acid or glycol) Malic acid PEG400: PEG#400 (trade name, Lion Corporation, polyethylene glycol)

[0133] (Crosslinking agent) WS-500...Epocross (registered trademark) WS-500 (trade name, Nippon Shokubai Co., Ltd., oxazoline group-containing compound, solid content: 39% by mass) #220: Fixer #220 (product name, Murayama Chemical Laboratory Co., Ltd., isocyanate group-containing compound with an isocyanurate skeleton in its structure, solid content: 40% by mass)

[0134] [Table 2]

[0135] [Table 3]

[0136] 3. Preparation of Inkjet Ink Composition [Cyan ink] The components were placed in a mixing tank and mixed and stirred for 2 hours using a stirrer to obtain the composition shown in Table 4. The mixture was then filtered through a membrane filter with a pore size of 1 μm to obtain a cyan ink (hereinafter also referred to as "C ink") as an ink composition. The numerical values ​​for each component in Table 4 represent mass %. "C ink" indicates cyan ink.

[0137] The components shown in Table 4 are as follows:

[0138] (dye dispersant) Disperse Blue 359: CI Disperse Blue 359 (commercially available)

[0139] (Water-soluble organic solvent) Propylene glycol Glycerin Methyl triglycol

[0140] (Surfactant) BYK(R)-348: BYK(registered trademark)-348 (trade name, silicone surfactant, manufactured by BYK Japan Co., Ltd.)

[0141] [Table 4]

[0142] 4. Preparation of printed materials 4.1. Preparation of fabric with treatment liquid composition attached (Examples 1 to 11 and Comparative Examples 2 to 5) The treatment liquid composition was adhered to fabric using each of the treatment liquid compositions of Examples 1 to 11 and Comparative Examples 2 to 5. Specifically, fabrics to which the treatment liquid composition was adhered were obtained as follows. The fabric was prepared by immersing a white cotton braid #4000 (product name, manufactured by Toyobo Co., Ltd.) in the treatment liquid composition, and applying the treatment liquid composition to the fabric with a mangle roller so that the wringing rate was 80%. The fabric was then dried at 140°C for 2 minutes and further dried at 170°C for 1 minute to obtain fabrics with the treatment liquid composition adhered thereto.

[0143] The drawing rate (S) was calculated by the following formula (1). S(%)=〔(AB) / B〕×100...(1) In the formula (1), S represents the wringing rate (%), A represents the mass of the fabric to which the treatment liquid composition has been applied, and B represents the mass of the fabric before the treatment liquid composition has been applied.

[0144] 4.2. Preparation of intermediate recording medium with ink composition attached (Examples 1 to 11 and Comparative Examples 1 to 5) The ink C was filled into the cartridge of an inkjet printer PX-G930 (trade name, manufactured by Seiko Epson Corporation). Then, the ink was applied to a coated surface of coated paper (TRANSJET Sportline 1254 (trade name), manufactured by Chem Paper Co.) as an intermediate transfer medium at a resolution of 720 dpi x 720 dpi with an ink ejection rate of 12 mg / inch at a 100% duty ink ejection rate. 2 An image having a solid pattern was formed by depositing the ink composition under the conditions of (a) to (c) above. This gave an intermediate recording medium having the ink composition deposited thereon.

[0145] 4.3.Textile printing (Examples 1 to 11 and Comparative Examples 2 to 5) The image-formed surface of the intermediate recording medium to which the ink composition was adhered obtained above was then pressed onto the fabric (cotton blade) to which the treatment liquid composition was adhered obtained above, using a heat press machine TP-608M (trade name, manufactured by Taiyo Seiki Co., Ltd.) at a temperature of 200°C and a pressure of 4.2 N / cm. 3 The ink was thermally transferred for 60 seconds and 60 seconds, and printed fabrics with ink C attached were obtained.

[0146] (Comparative Example 1) The surface of the intermediate recording medium with the ink composition adhered thereto obtained above, on which the image was formed, was pressed onto a white cotton blade #4000 (trade name, manufactured by Toyobo Co., Ltd.), which is a fabric, using a heat press machine TP-608M (trade name, manufactured by Taiyo Seiki Co., Ltd.) at a temperature of 200°C and a pressure of 4.2 N / cm. 3 The ink was thermally transferred for 60 seconds and 60 seconds to obtain a printed fabric having ink C attached thereto.

[0147] 5. Evaluation of printed items 5.1.Color development The printed textiles obtained by the above-mentioned textile printing in Examples 1 to 11 and Comparative Examples 1 to 5 were each left to stand for 3 days at a room temperature of 25° C. Thereafter, the color density (OD value) of each of the printed textiles after standing to C ink was measured using a fluorescent spectrodensitometer FD-7 (trade name, manufactured by Konica Minolta, Inc.) under the following measurement conditions at a room temperature of 25° C. (Measurement conditions) Observation light source: D65 Field of view: 2° Status: T Polarizing filter: Not installed

[0148] Thereafter, the OD values ​​for the printed materials in Examples 1 to 11 and Comparative Examples 2 to 5 were compared with the OD value for the printed material in Comparative Example 1, and the color development with C ink was evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6. (Evaluation criteria) AA: Compared with the OD value for the printed material in Comparative Example 1, the OD value was 220% or more. A: Compared with the OD value for the printed material in Comparative Example 1, the OD value was 150% or more and less than 220%. B: Compared with the OD value for the printed material in Comparative Example 1, the OD value was 100% or more and less than 150%. C: Compared with the OD value for the printed material in Comparative Example 1, the OD value was less than 100%.

[0149] 5.2.Texture The texture of each of the printed textiles obtained by the above-mentioned textile printing in Examples 1 to 11 and Comparative Examples 1 to 5 was evaluated by a sensory test. Specifically, judges performed a sensory evaluation of the feel of the obtained printed textiles and evaluated the texture according to the following criteria. The results are shown in Tables 5 and 6. (Evaluation criteria) A: The printed material is soft and does not feel stiff. B: The printed material is slightly hard and feels a little stiff to the touch. C: The printed material is hard and has a significantly stiff feel.

[0150] 5.3.Abrasion resistance The printed textiles obtained by the above-described textile printing in Examples 1 to 11 and Comparative Examples 1 to 5 were left to stand for 1 hour at a room temperature of 25°C. Then, the printed surface of the printed textile was evaluated for abrasion resistance using a Gakushin-type abrasion fastness tester AB-301 (trade name, manufactured by Tester Sangyo Co., Ltd.) in accordance with JIS K5701:2000. Specifically, a cotton cloth was placed on the printed surface and rubbed 20 times with a 200 g load. After rubbing, peeling of the printed surface and transfer of ink to the cotton cloth were visually confirmed, and abrasion resistance was evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6. (Evaluation criteria) A: Neither color transfer nor peeling was observed. B: Slight color transfer and peeling were observed. C: Color transfer and peeling were clearly observed.

[0151] 5.4. Washing fastness The printed textiles obtained by the above-described textile printing in Examples 1 to 11 and Comparative Examples 1 to 5 were subjected to a washing fastness test in accordance with Method A-2 of JIS L0844 (Testing method for color fastness to washing). Specifically, the printed textiles obtained by the above-described textile printing in Examples 1 to 11 and Comparative Examples 1 to 5 were washed in a household washing machine (ZABOON (trade name), manufactured by Toshiba Corporation) using a general household laundry detergent (fluorescent brightener-free), rinsed, dehydrated, and dried, and then the discoloration of the printed textiles was evaluated. Discoloration was evaluated according to the discoloration gray scale of JIS L0804:2004 (ISO 105-C10(B2)), and the degree of discoloration was evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6. (Evaluation criteria) A: Washing fastness is grade 3 or higher. B: Washing fastness is grade 2 or more but less than grade 3. C: Washing fastness is less than grade 2.

[0152] 5.5.Discoloration The printed textiles of Examples 1 to 11 and Comparative Examples 1 to 5 obtained by the above-mentioned textile printing were left to stand for 1 hour at a room temperature of 25° C. Then, using a fluorescence spectrodensitometer FD-7 (trade name, manufactured by Konica Minolta, Inc.), the color density (OD value) of each of the printed textiles after standing was measured for C ink under the following measurement conditions at a room temperature of 25° C. Then, each of the printed textiles was left to stand for 3 days at a room temperature of 25° C., and the color density (OD value) of each of the printed textiles after standing was measured under the same conditions. (Measurement conditions) Observation light source: D65 Field of view: 2° Status: T Polarizing filter: Not installed

[0153] The OD value of the printed textile immediately after printing was compared with the OD value of the printed textile after being left for 3 days, and the discoloration and fading of the printed textiles in Examples 1 to 11 and Comparative Examples 1 to 5 were evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6. (Evaluation criteria) A: The rate of change in OD value was less than 5%. B: The rate of change in OD value was 5% or more and less than 10%. C: The rate of change in OD value was 10% or more.

[0154] [Table 5]

[0155] [Table 6]

[0156] As shown in Tables 5 and 6, it was found that by applying the treatment liquid composition of this embodiment to fabric and then printing the fabric to which the treatment liquid composition has been applied, it is possible to obtain a printed textile having excellent color development and good texture.

[0157] Comparing Examples 1, 4, and 6 with Examples 2, 3, and 5, it was found that when a polyester resin having a glass transition temperature of 50° C. or higher was used, printed materials with better discoloration resistance could be obtained.

[0158] Comparing Examples 1, 4, and 11 with Example 2, it was found that when a polyester resin having a molar ratio of the content of isophthalic acid-derived structural units to the content of terephthalic acid-derived structural units in the range of 0.5 to 3.0 is used, printed materials with better color development and color resistance can be obtained.

[0159] Comparing Examples 7 and 8 with Example 1, it was found that the use of a crosslinking agent resulted in printed textiles with superior color development and abrasion resistance.

Claims

1. A treatment liquid composition to be applied to a fabric, A polyester resin and water are included, the polyester resin has a structural unit derived from an aromatic compound and a structural unit derived from a non-aromatic compound, the aromatic compound comprises phthalic acid, the non-aromatic compound comprises a (poly)alkylene glycol; the content of the structural unit derived from phthalic acid is 15 mol% or more and 85 mol% or less relative to 100 mol% of the polyester resin, the content of the (poly)alkylene glycol-derived structural unit is 15 mol % or more and 85 mol % or less relative to 100 mol % of the polyester resin; the phthalic acid-derived structural units include terephthalic acid-derived structural units and isophthalic acid-derived structural units, the molar ratio of the content of the structural units derived from isophthalic acid to the content of the structural units derived from terephthalic acid is 0.5 or more and 3.0 or less; A processing liquid composition for dye printing.

2. 2. The dye printing treatment liquid composition according to claim 1, wherein the (poly)alkylene glycol is at least one selected from the group consisting of ethylene glycol, neopentyl glycol, and diethylene glycol.

3. The dye textile printing treatment liquid composition according to claim 1 or 2, wherein the polyester resin has a glass transition temperature of 50° C. or higher.

4. The dye textile printing treatment liquid composition according to any one of claims 1 to 3, wherein the fabric contains a fiber having a hydroxyl group.

5. The dye textile printing treatment liquid composition according to any one of claims 1 to 4, further comprising a crosslinking agent.

6. The dye textile printing treatment liquid composition according to claim 5, wherein the crosslinking agent comprises an isocyanate group-containing compound having an isocyanurate skeleton in its structure.

7. 7. The dye printing treatment liquid composition according to claim 1, wherein the content of the polyester resin is from 0.05% by mass to 20% by mass, both inclusive, based on the total amount of the treatment liquid composition.

8. The dye textile printing treatment liquid composition according to any one of claims 1 to 7, which is used to be adhered to the fabric before the fabric is dye-printed.

9. A method for producing a dye textile printing apparatus, comprising the dye textile 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 textile printing method, comprising a treatment liquid composition applying step of applying the dye textile printing treatment liquid composition according to any one of claims 1 to 8 to a fabric.

11. a treatment liquid composition applying step of applying the dye textile printing treatment liquid composition provided in the composition set according to claim 9 to a fabric; a discharge step of discharging the inkjet ink composition provided in the composition set according to claim 9 from a recording head and depositing the ink on an intermediate transfer medium; a transfer step of transferring the inkjet ink composition adhered to the intermediate transfer medium to the fabric to which the dye textile printing treatment liquid composition has been adhered, Inkjet printing method.

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