Pretreatment solution and printing method for textile printing

Abstract

To provide a pre-treatment solution for textile printing that can improve the colorfastness, texture, and washability of printed materials. [Solution] A pre-treatment solution for textile printing according to one embodiment of the present invention comprises a polyester resin (A) obtained by polycondensation of an alcohol component and a carboxylic acid component, a crosslinking agent, and water, wherein the carboxylic acid component contains phthalic acid, the acid value of the polyester resin (A) is 5 to 40 mgKOH / g, the aromatic ring concentration of the polyester resin (A) is 4.20 to 5.20 mol / kg, and the glass transition temperature of the polyester resin (A) is 0 to 40°C.

Description

[Technical Field]

[0001] The present invention relates to a pretreatment solution for textile printing and a textile printing method. [Background technology]

[0002] Conventionally, when dyeing fabrics with colorants to manufacture printed materials, a technique has been known in which the fabric is pre-treated with a resin-containing treatment solution to improve the color development and washability of the printed materials, and various studies have been conducted on the resins contained in the treatment solution.

[0003] For example, Patent Document 1 describes an aqueous dispersion of polyester resin obtained by finely dispersing polyester resin in an aqueous medium. Patent Document 2 also describes a pretreatment liquid consisting of an aqueous composition containing resin, which is applied to polyester fabric. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2011-099125 [Patent Document 2] Japanese Patent Publication No. 2009-249773 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, it is difficult to achieve good colorfastness, texture, and washability in all aspects of printed materials. [Means for solving the problem]

[0006] One embodiment of the pretreatment solution for textile printing according to the present invention is: A pre-treatment solution for textile printing comprising a polyester resin (A) obtained by polycondensation of an alcohol component and a carboxylic acid component, a crosslinking agent, and water, The carboxylic acid component contains phthalic acid, the acid value of the polyester resin (A) is 5 to 40 mg KOH / g, the aromatic ring concentration of the polyester resin (A) is 4.20 to 5.20 mol / kg, and the glass transition temperature of the polyester resin (A) is 0 to 40°C.

[0007] One embodiment of the printing method according to the present invention is: A coating step of applying the pre-treatment solution for printing according to one embodiment described above to the fabric, A drying step in which the fabric to which the pre-treatment solution for printing has been applied is dried by heating, A recording process in which an ink composition containing a disperse dye and water is ejected from an inkjet head and deposited onto an intermediate transfer medium for recording, The process includes a transfer step of transferring the ink composition adhering to the intermediate transfer medium to the fabric to which the pre-treatment solution for printing has been applied. [Brief explanation of the drawing]

[0008] [Figure 1] Table 1 shows the composition and evaluation results of the pretreatment solutions used for printing in each example. [Figure 2] Table 2 shows the composition of the polyester resin used in each example. [Modes for carrying out the invention]

[0009] Embodiments of the present invention will be described below. The embodiments described below are examples of the present invention. The present invention is not limited in any way to the embodiments described below, and includes various modifications that can be implemented without changing the gist of the present invention. Not all of the configurations described below are necessarily essential to the present invention.

[0010] In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively.

[0011] 1. Pretreatment solution for textile printing The pretreatment liquid for printing and dyeing according to an embodiment of the present invention is a pretreatment liquid for printing and dyeing containing a polyester resin (A) obtained by polycondensing an alcohol component and a carboxylic acid component, a crosslinking agent, and water, wherein the carboxylic acid component contains phthalic acid, the acid value of the polyester resin (A) is 5 to 40 mgKOH / g, the aromatic ring concentration of the polyester resin (A) is 4.20 to 5.20 mol / kg, and the glass transition temperature of the polyester resin (A) is 0 to 40 °C.

[0012] When the aromatic ring concentration in the polyester resin is increased, the interaction with the aromatic ring structure that the disperse dye contained in the ink composition may have is strengthened, so the color fading resistance and washability of the printed and dyed product are improved. On the other hand, when the aromatic ring concentration increases, the rigidity of the molecular chain increases, so the glass transition temperature of the polyester resin rises, the resin becomes hard, and the texture deteriorates. Thus, conventionally, it has been difficult to achieve both the color fading resistance and washability of the printed and dyed product and the texture of the printed and dyed product.

[0013] Therefore, as a result of intensive studies, by using phthalic acid (orthophthalic acid) with low molecular symmetry as the carboxylic acid component in the polyester resin, even when the aromatic ring concentration is increased, an increase in the rigidity of the molecular chain can be reduced, that is, an increase in the glass transition temperature can be suppressed. Thereby, it is possible to adjust the aromatic ring concentration and the glass transition temperature of the polyester resin contained in the pretreatment liquid for printing and dyeing to a desired range, and achieve both the color fading resistance and washability of the printed and dyed product and the texture of the printed and dyed product.

[0014] Hereinafter, each component contained in the pretreatment liquid for printing and dyeing according to the present embodiment will be described.

[0015] 1.1 Polyester resin (A) The pretreatment liquid for printing and dyeing according to the present embodiment contains a polyester resin (A) obtained by polycondensing an alcohol component and a carboxylic acid component.

[0016] The content of polyester resin (A) (in terms of solids) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, particularly preferably 2.0% by mass or more, even more preferably 3.0% by mass or more, and especially preferably 4.0% by mass or more, relative to the total amount of the pretreatment solution for printing. Furthermore, the upper limit of the polyester resin (A) content (in terms of solids) is not particularly limited, but it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, particularly preferably 10% by mass or less, and most particularly preferably 7% by mass or less, relative to the total amount of the pretreatment solution for printing.

[0017] When the polyester resin (A) content is 1% by mass or more in terms of solid content relative to the total amount of the pre-treatment solution for printing, the color development and washability of the printed fabric tend to improve. Also, when the polyester resin (A) content is 20% by mass or less in terms of solid content relative to the total amount of the pre-treatment solution for printing, the texture of the printed fabric tends to improve.

[0018] 1.1.1 Alcohol content Examples of alcohol components include diols (x1) and polyols with a valentity of 3 or higher (x2). These may be used individually or in combination of two or more types.

[0019] Examples of diols (x1) include alkylene glycols with 2 to 36 carbon atoms (ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol, etc.) and alkylene ether glycols with 4 to 36 carbon atoms (diethylene glycol, triethylene glycol) Examples include dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol, etc., alicyclic diols having 6 to 36 carbon atoms (such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A), (poly)alkylene oxide adducts of the above alicyclic diols (preferably with an average number of added moles of 1 to 30), aromatic diols [monocyclic divalent phenols (e.g., hydroquinone) and bisphenols, etc.], and alkylene oxide adducts of the above aromatic diols (preferably with an average number of added moles of 2 to 30).

[0020] The alkylene oxide adducts of the above-mentioned bisphenols are obtained by adding alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as AO) to bisphenols.

[0021] Examples of bisphenols include those represented by the following general formula (1). HO-Ar-P-Ar-OH (1) [In the formula, P represents an alkylene group having 1 to 3 carbon atoms, -SO2-, -O-, -S-, or a direct bond, and Ar represents a phenylene group in which a hydrogen atom may be substituted with a halogen atom or an alkyl group having 1 to 30 carbon atoms.]

[0022] Specific examples of bisphenols include bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A, and 2,2'-diethylbisphenol F, and two or more of these can be used in combination.

[0023] Examples of alkylene oxides to be added to bisphenols include alkylene oxides having 2 to 30 carbon atoms, such as ethylene oxide (hereinafter, "ethylene oxide" may be abbreviated as EO), propylene oxide ("propylene oxide" may be abbreviated as PO), butylene oxide, tetrahydrofuran, and combinations of two or more of these.

[0024] Of these diols (x1), from the viewpoint of solvent solubility of polyester resin (A), preferably alkylene glycols having 2 to 36 carbon atoms, alkylene oxide adducts of aromatic diols, more preferably alkylene glycols having 2 to 10 carbon atoms, alkylene oxide adducts of bisphenols (average number of added moles preferably 2 to 5), even more preferably alkylene glycols having 2 to 10 carbon atoms, alkylene oxide adducts of bisphenol A (average number of added moles preferably 2 to 5), particularly preferably alkylene glycols having 2 to 10 carbon atoms, and most preferably alkylene glycols having 2 to 6 carbon atoms.

[0025] Examples of polyols with a valency of 3 or higher (x2) include aliphatic polyhydric alcohols with 3 to 36 carbon atoms and a valency of 3 or higher, sugars and their derivatives, alkylene oxide adducts of aliphatic polyhydric alcohols (average number of added moles is preferably 1 to 30), alkylene oxide adducts of trisphenols (such as trisphenol PA) (average number of added moles is preferably 2 to 30), and alkylene oxide adducts of novolac resins (which include phenol novolac and cresol novolac, and have an average degree of polymerization of preferably 3 to 60) (average number of added moles is preferably 2 to 30).

[0026] Examples of aliphatic polyhydric alcohols with 3 to 36 carbon atoms and a valency of 3 or higher include alkane polyols and their intramolecular or intermolecular dehydrated products, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol. Examples of sugars and their derivatives include sucrose and methyl glucoside.

[0027] Of these trivalent or higher polyols (x2), from the viewpoint of exhibiting superior colorfastness of printed materials, aliphatic polyhydric alcohols with 3 to 36 carbon atoms and a valency of trivalent or higher are preferred, more preferably trivalent aliphatic polyhydric alcohols with 3 to 8 carbon atoms, and particularly preferred is trimethylolpropane.

[0028] The amount of diol (x1) in the alcohol component of polyester resin (A) is preferably 90 to 99.9 mol%, and more preferably 95 to 99.8 mol%, from the viewpoint of solvent solubility when producing an aqueous dispersion of polyester resin (A). When containing a trivalent or higher polyol (x2), the amount of the trivalent or higher polyol (x2) in the alcohol component of the polyester resin (A) is preferably 0.1 to 10 mol%, and more preferably 0.2 to 5 mol%, from the viewpoint of solvent solubility and discoloration resistance during the production of an aqueous dispersion of the polyester resin (A).

[0029] In one embodiment, the alcohol component can be derived from biomass-based raw materials. Biomass-based raw materials refer to raw materials derived from plants and microorganisms.

[0030] Examples of alcohol components derived from biomass include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, and neopentyl glycol.

[0031] Furthermore, the polyester resin (A) may contain a monool component in addition to the polyol component as needed. Examples of monools include linear or branched alkyl alcohols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, 1-decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol, etc.).

[0032] Of these monools, linear or branched alkyl alcohols having 8 to 24 carbon atoms are preferred from the viewpoint of exhibiting superior colorfastness of printed materials, linear alkyl alcohols having 8 to 24 carbon atoms are more preferred, and dodecyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol are even more preferred.

[0033] 1.1.2 Carboxylic Acid Components The carboxylic acid component in polyester resin (A) contains phthalic acid. The inclusion of phthalic acid in the carboxylic acid component results in an ortho orientation position, giving the resulting polyester resin a bent molecular chain structure. When used as a treatment agent for dye printing, this is thought to facilitate the incorporation of disperse dyes into the polyester resin's molecular chains during heat transfer, resulting in excellent color development. Furthermore, the asymmetric structure of the skeleton inhibits molecular chain rotation, which is thought to facilitate the fixation of dyes into the polyester resin during storage at room temperature, even when the glass transition temperature of the polyester resin is near or below room temperature, thus providing excellent colorfastness. Furthermore, it is preferable from the viewpoint of colorfastness that the polyester resin (A) contains a carboxylic acid component other than phthalic acid. Other carboxylic acid components besides phthalic acid include dicarboxylic acids other than phthalic acid (y1) and polycarboxylic acids with a valency of 3 or higher (y2). These may be used individually or in combination of two or more types. Note that phthalic acid refers to orthophthalic acid, and may also be phthalic anhydride, alkyl (methyl, ethyl, butyl, and stearyl with 1 to 24 carbon atoms, preferably with 1 to 4 carbon atoms) esters, and partially alkyl esters.

[0034] Examples of dicarboxylic acids other than phthalic acid (y1) include aromatic dicarboxylic acids having 8 to 36 carbon atoms (isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid, etc.), aliphatic dicarboxylic acids having 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, reparginic acid, and sebacic acid, etc.), alicyclic dicarboxylic acids having 6 to 40 carbon atoms (dimeric acid (dimerized linoleic acid), etc.), alkenedicarboxylic acids having 4 to 36 carbon atoms (alkenyl succinic acids such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, and mesaconic acid, etc.), and their ester-forming derivatives. Here, ester-forming derivatives refer to carboxylic acid anhydrides, alkyl (methyl, ethyl, butyl, and stearyl having 1 to 24 carbon atoms, preferably having 1 to 4 carbon atoms) esters, and partially alkyl esters.

[0035] Of these dicarboxylic acids (y1), from the viewpoint of exhibiting superior colorfastness of printed materials, preferred are aromatic dicarboxylic acids having 8 to 36 carbon atoms, aliphatic dicarboxylic acids having 2 to 50 carbon atoms, and alkene dicarboxylic acids having 4 to 36 carbon atoms. More preferably are isophthalic acid, terephthalic acid, adipic acid, succinic acid, maleic acid, and fumaric acid. Even more preferably are isophthalic acid and terephthalic acid, and particularly preferably isophthalic acid. These acids may also be anhydrides or lower alkyl esters.

[0036] Examples of polycarboxylic acids with a valency of 3 or higher (y2) include aromatic polycarboxylic acids with 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), aliphatic (including alicyclic) tricarboxylic acids with 6 to 36 carbon atoms (such as hexanetricarboxylic acid and decanetricarboxylic acid), and ester-forming derivatives thereof.

[0037] Of these trivalent or greater polycarboxylic acids (y2), aromatic polycarboxylic acids having 9 to 20 carbon atoms are preferred from the viewpoint of solubility, with trimellitic acid and pyromellitic acid being more preferred. Furthermore, anhydrides or lower alkyl esters of these acids may also be used.

[0038] The phthalic acid content in the carboxylic acid component of polyester resin (A) is preferably 1 mol% or more, more preferably 20 mol% or more, and particularly preferably 40 mol% or more, from the viewpoint of having superior color development of printed materials. When a dicarboxylic acid other than phthalic acid (y1) is included, the content of the dicarboxylic acid other than phthalic acid (y1) in the carboxylic acid component of the polyester resin (A) is preferably 99 mol% or less, more preferably 80 mol% or less, and particularly preferably 60 mol% or less, from the viewpoint of having superior color development of the printed material. When the carboxylic acid component includes isophthalic acid in addition to phthalic acid, the molar ratio of phthalic acid to isophthalic acid (phthalic acid:isophthalic acid) is preferably 1:99 to 99:1, more preferably 20:80 to 99:1, and particularly preferably 40:60 to 99:1, from the viewpoint of having superior color development and color fading properties in printed materials.

[0039] In one embodiment, dicarboxylic acids other than phthalic acid (y1) can be derived from biomass. Biomass-derived raw materials refer to raw materials derived from plants and microorganisms.

[0040] Examples of biomass-derived dicarboxylic acids include malonic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, and dimer acid.

[0041] Furthermore, the polyester resin (A) may contain monocarboxylic acid components as needed. Examples of monocarboxylic acids include aromatic monocarboxylic acids with 7 to 37 carbon atoms (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.) and aliphatic (including alicyclic) monocarboxylic acids with 2 to 50 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, and behenic acid, etc.).

[0042] Among these monocarboxylic acids, aromatic monocarboxylic acids having 7 to 37 carbon atoms are preferred, and benzoic acid is more preferred, from the viewpoint of exhibiting superior resistance to discoloration of printed materials.

[0043] 1.1.3 Physical Properties The aromatic ring concentration of polyester resin (A) is 4.20 to 5.20 mol / kg, preferably 4.30 to 5.10 mol / kg, and more preferably 4.60 to 5.00 mol / kg. If the aromatic ring concentration of (A) is less than 4.20 mol / kg, the discoloration resistance decreases, and if it exceeds 5.20 mol / kg, the storage stability decreases. The aromatic ring concentration of polyester resin (A) is calculated using the following formula. [Aromatic ring concentration (mol / kg)] = [Amount of aromatic rings (mol) when all raw materials of polyester resin (A) have reacted] / [Total mass (kg) of raw materials constituting polyester resin (A) - Amount of ester bonds (mol) when all raw materials of polyester resin (A) have reacted × 18 × 10 -3 ] The aromatic ring concentration of polyester resin (A) can be adjusted by adjusting the aromatic ring concentration and content of the alcohol component and the carboxylic acid component.

[0044] The ester group concentration of the polyester resin (A) is preferably 8.2 to 10.4 mol / kg, more preferably 8.8 to 10.2 mol / kg, and even more preferably 9.2 to 10.0 mol / kg. If the ester group concentration of (A) is 8.2 mol / kg or higher, the discoloration resistance is good, and if it is 10.4 mol / kg or lower, the solvent solubility of the polyester resin (A) tends to be good. The ester group concentration of polyester resin (A) is calculated using the following formula. [Ester group concentration (mol / kg)] = [Amount of ester bonds when all the raw materials of polyester resin (A) react (mol)] / [Total mass of raw materials constituting polyester resin (A) (kg) - Amount of ester bonds when all the raw materials of polyester resin (A) react (mol) × 18 × 10 -3 ] The ester group concentration of polyester resin (A) can be adjusted by adjusting the molar concentration of hydroxyl groups and ester groups of the alcohol component, as well as the molar concentration of carboxyl groups and ester groups of the carboxylic acid component.

[0045] The acid value of polyester resin (A) is 5 to 40 mgKOH / g, preferably 6 to 30 mgKOH / g, and more preferably 7 to 25 mgKOH / g. If the acid value of polyester resin (A) is less than 5 mgKOH / g, the particle size of polyester resin (A) increases and storage stability deteriorates, and if it exceeds 40 mgKOH / g, the amount of components that dissolve in the water medium increases and storage stability deteriorates. In this application, the acid value of polyester resin (A) refers to the acid value of the free acid (carboxyl group) before neutralization when polyester resin (A) is neutralized with alkali. From the viewpoint of storage stability, the hydroxyl value of polyester resin (A) is preferably 0 to 40 mg KOH / g, more preferably 0.1 to 30 mg KOH / g, and even more preferably 0.1 to 25 mg KOH / g. If it exceeds 40 mg KOH / g, the amount of components that dissolve in the water medium increases, and storage stability deteriorates. The acid value and hydroxyl value can be measured by the method specified in JIS K0070.

[0046] The glass transition temperature (Tg) of polyester resin (A) is 0 to 40°C, preferably 5 to 35°C, and more preferably 10 to 30°C. If the Tg of polyester resin (A) is below 0°C, the discoloration resistance decreases, and if it exceeds 40°C, the texture deteriorates. The glass transition temperature (Tg) of polyester resin (A) can be appropriately adjusted depending on the type and amount of each raw material component used, as well as manufacturing conditions such as reaction temperature, reaction time, and cooling rate. The glass transition temperature (Tg) of polyester resin (A) can be measured by the method specified in ASTM D3418-82 (DSC method). For measuring the glass transition temperature (Tg), for example, a DSC Q20 manufactured by TA Instruments Co., Ltd. can be used. The glass transition temperature (Tg) can be measured under the following conditions. <Measurement conditions> (1) Increase the temperature from 30°C to 150°C at a rate of 20°C / min. (2) Hold at 150°C for 10 minutes (3) Cool to -35°C at 20°C / min (4) Hold at -35°C for 10 minutes. (5) Heat up to 150°C at a rate of 20°C / min (6) The differential scanning calorimetry curve measured in process (5) is analyzed, and the position of the inflection point is defined as the glass transition temperature.

[0047] The peak-top average molecular weight of polyester resin (A) is preferably 3,000 to 20,000, more preferably 7,500 to 20,000, and even more preferably 10,000 to 20,000, from the viewpoint of storage stability and resistance to discoloration.

[0048] In the present invention, the peak-top average molecular weight can be measured using gel permeation chromatography (GPC) under the following conditions. Equipment (example): HLC-8120 manufactured by Tosoh Corporation Column (example): TSK GEL GMH6 (2 pieces) [Manufactured by Tosoh Corporation] Measurement temperature: 40℃ Sample solution: 0.25% by weight THF solution Solution injection volume: 100μL Detection device: Refractive index detector Reference material: 12 samples of standard polystyrene (TSKstandard POLYSTYRENE) manufactured by Tosoh Corporation (molecular weights: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,890,000) To measure the molecular weight, the sample is dissolved in tetrahydrofuran (THF) to a concentration of 0.25% by weight, and the undissolved portion is filtered out using a PTFE filter with a 220 nm aperture to obtain the sample solution.

[0049] In one embodiment, the biomass concentration in the polyester resin (A) is preferably 1% by weight or more, more preferably 10% by weight or more, and even more preferably 20% by weight or more, from the viewpoint of resolving the depletion of petroleum resources and considering the environment. The above biomass concentration refers to the weight ratio (percentage) of constituent monomers derived from biomass to the total amount of alcohol components and carboxylic acid components, excluding PET flakes from the polyester resin (A).

[0050] 1.1.4 Manufacturing method A method for producing polyester resin (A) will be described. Polyester resin (A) can be obtained by mixing an alcohol component and a carboxylic acid component containing phthalic acid, and carrying out a polycondensation reaction in the presence of a polymerization catalyst. Furthermore, the ethylene glycol and terephthalic acid components contained in the polyester resin (A) may be derived from PET (polyethylene terephthalate). In this case, the polyester resin (A) can be obtained by mixing PET with other alcohol and carboxylic acid components and carrying out a polycondensation reaction in the presence of a polymerization catalyst.

[0051] Specifically, polyester resin (A) can be manufactured, for example, as follows: For example, an alcohol component and a carboxylic acid component are subjected to a polycondensation reaction in an inert gas (such as nitrogen gas) atmosphere at a reaction temperature of preferably 150 to 280°C, more preferably 160 to 250°C, and even more preferably 170 to 235°C, from the viewpoint of polycondensation reactivity and resin coloring.

[0052] Furthermore, as mentioned above, PET may be mixed together with the alcohol component and the carboxylic acid component.

[0053] An esterification catalyst can be used as needed at this time. Examples of esterification catalysts include tin-containing catalysts (e.g., dibutyltin oxide), antimony trioxide, titanium-containing catalysts [e.g., titanium alkoxides (e.g., tetrabutoxytitanate), potassium titanate oxalate, titanium terephthalate, titanium terephthalate alkoxide, catalysts described in Japanese Patent Publication No. 2006-243715 {titanium diisopropoxybis(triethanolamine), titanium dihydroxybis(triethanolamine), titanium monohydroxytris(triethanolamine), titanylbis(triethanolamine) and their intramolecular polycondensates, etc.} and catalysts described in Japanese Patent Publication No. 2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate and titanium diisopropoxyditeterephthalate, etc.)], zirconium-containing catalysts (e.g., zirconyl acetate), and zinc acetate. Among these, titanium-containing catalysts are preferred.

[0054] Furthermore, stabilizers may be added to ensure stable polymerization of polyester. Examples of stabilizers include hydroquinone, methylhydroquinone, and hindered phenol compounds.

[0055] 1.1.5 Resin aqueous dispersion The polyester resin (A) may be used as an aqueous resin dispersion in an aqueous medium. The aqueous medium is a medium containing at least water and may also contain an organic solvent. Such an organic solvent can be the same as the organic solvent (described later) used in the organic solvent solution of the polyester resin (A) obtained by the above manufacturing method.

[0056] There are no particular restrictions on the method for producing an aqueous dispersion of polyester resin (A), as long as it includes a step of mixing an organic solvent solution of polyester resin (A) with an aqueous medium.

[0057] Examples of methods for producing an aqueous resin dispersion containing polyester resin (A) include the following method [1].

[0058] [1] A method for producing a polyester resin solution by dissolving polyester resin (A) in an organic solvent, then, if necessary, dispersing the carboxyl groups of the polyester resin as salts with a neutralizing agent such as potassium hydroxide in an aqueous medium, and then distilling off the organic solvent if necessary.

[0059] In the case of [1], in the step of dispersing the polyester resin (A) in an aqueous medium, it is preferable to use a rotary dispersion and mixing apparatus as described later, and the temperature is preferably 60°C or lower, and more preferably 40°C or lower, from the viewpoint of storage stability. The dispersion time can be appropriately selected depending on the apparatus used, but is generally preferably 1 minute to 2 hours, and more preferably 3 minutes to 1 hour.

[0060] In a method for producing an aqueous dispersion of a resin, examples of organic solvents for the organic solvent solution of polyester resin (A) include aromatic hydrocarbon solvents, aliphatic or alicyclic hydrocarbon solvents, halogen solvents, esters, ester ether solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic compound solvents, and mixed solvents of two or more of these. Specific examples of organic solvents include aromatic hydrocarbon solvents (toluene, xylene, ethylbenzene, and tetralin, etc.); aliphatic or alicyclic hydrocarbon solvents (n-hexane, n-heptane, mineral spirits, and cyclohexane, etc.); halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylenedichloride, carbon tetrachloride, trichloroethylene, and perchloroethylene; ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate; diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl acetate Examples of organic solvents include ether solvents such as Rosolve and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, and benzyl alcohol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methylpyrrolidone; and mixed solvents of two or more of these. Among the above organic solvents, volatile ones with a boiling point of less than 100°C are preferred. Preferred organic solvents include ethyl acetate, acetone, isopropanol, tetrahydrofuran, and methyl ethyl ketone.

[0061] The amount of organic solvent used per 100 parts by weight of polyester resin (A) is preferably 25 to 300 parts by weight, more preferably 25 to 150 parts by weight, and even more preferably 25 to 100 parts by weight, from the viewpoint of solvent solubility of the resin.

[0062] In the method for producing an aqueous resin dispersion, the aqueous medium used in the step of mixing an organic solvent solution of polyester resin (A) with an aqueous medium can be any liquid in which water is an essential component, and can be water, an aqueous solution of an organic solvent, an aqueous solution of a surfactant (s) as described later, an aqueous solution of a water-soluble polymer (t), or a mixture of two or more of these.

[0063] To improve the dispersibility of polyester resin (A) in an aqueous medium, a neutralizing agent may be used to neutralize the carboxyl groups of polyester resin (A). Examples of neutralizing agents include organic compounds such as ammonia and triethylamine, and inorganic compounds such as potassium hydroxide and sodium hydroxide.

[0064] The amount of neutralizing agent used is preferably 1 to 150 mol%, more preferably 5 to 100 mol%, relative to the carboxyl groups of the polyester resin (A), from the viewpoint of dispersibility.

[0065] When dispersing the polyester resin (A) in an aqueous medium, known surfactants (s) and inorganic dispersants can be used as emulsifiers or dispersants as needed.

[0066] The surfactant (s) is not particularly limited and includes anionic surfactants (s-1), cationic surfactants (s-2), amphoteric surfactants (s-3), and nonionic surfactants (s-4). The surfactant (s) may also be a combination of two or more surfactants.

[0067] Examples of anionic surfactants (s-1) include carboxylic acids or their salts, sulfate esters, carboxymethylated salts, sulfonates, and phosphate esters. Examples of cationic surfactants (S-2) include quaternary ammonium salt type surfactants and amine salt type surfactants. Examples of amphoteric surfactants (S-3) include carboxylate-type amphoteric surfactants, sulfate-type amphoteric surfactants, sulfonate-type amphoteric surfactants, and phosphate-type amphoteric surfactants. Examples of nonionic surfactants (s-4) include AO-added nonionic surfactants and polyhydric alcohol-type nonionic surfactants. Specific examples of these surfactants (s) include those described in Japanese Patent Publication No. 2002-284881.

[0068] Examples of inorganic dispersants include polyvalent metal phosphate salts such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; inorganic salts such as calcium metasilicate, calcium sulfate, and barium sulfate; and inorganic compounds such as magnesium hydroxide and aluminum hydroxide.

[0069] When dispersing polyester resin (A) in an aqueous medium, a known water-soluble polymer (t) can be used as an emulsifier or dispersant.

[0070] Examples of water-soluble polymers (t) include cellulose compounds (e.g., methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose and their saponified products), gelatin, starch, dextrin, acacia gum, chitin, chitosan, polyethylene glycol, and the like.

[0071] While there are no particular limitations on the dispersion method when mixing an organic solvent solution of polyester resin (A) with an aqueous medium, it is preferable to use a rotary dispersion mixer, an ultrasonic disperser, or a kneader, and among these, a rotary dispersion mixer, which has particularly excellent dispersion capabilities, is even more preferable.

[0072] Examples of rotary dispersion mixing devices include mixing devices with common agitators such as MaxBlend and helical blades, TK Homomixer [Primix Co., Ltd.], Creamix [M-Technique Co., Ltd.], Philmix [Primix Co., Ltd.], UltraTarlux [IKA Co., Ltd.], Ebara Milder [Ebara Corporation], Cavitron (Eurotech Co., Ltd.), and Biomixer [Nippon Seiki Co., Ltd.].

[0073] The amount of aqueous medium used per 100 parts by weight of the organic solvent solution of polyester resin (A) is preferably 100 to 500 parts by weight, more preferably 150 to 400 parts by weight, and even more preferably 150 to 300 parts by weight, from the viewpoint of storage stability.

[0074] The particle size of the particles in the aqueous dispersion of polyester resin (A) is preferably 30 to 250 nm, more preferably 30 to 200 nm, and particularly 30 to 190 nm, from the viewpoint of storage stability. In this invention, particle size refers to the cumulant average particle size. The particle size can be measured and determined by the light scattering measurement method described below. <Method for measuring particle size in an aqueous dispersion of polyester resin (A)> Cumulant analysis is performed using a zeta potential, particle size, and molecular weight measurement system [ELSZ-2000, manufactured by Otsuka Electronics Co., Ltd.], and the average particle size of the cumulant obtained from the measurement is taken as the average particle size of the polyester resin (A) in the aqueous resin dispersion. The measurement conditions are as follows: the dispersion of particles to be measured is placed in a measurement cell, the temperature is 25°C, the measurement angle is 165°, and the number of accumulations is 25. The refractive index of water (1.333) is input as the refractive index of the dispersion solvent. The dispersion is prepared by diluting the aqueous resin dispersion of polyester resin (A) 100 times with deionized water.

[0075] 1.2 Crosslinking agents The pre-treatment solution for textile printing according to this embodiment contains a crosslinking agent. By including a crosslinking agent in the pre-treatment solution for textile printing, crosslinking properties can be imparted, making it possible to bind the polyester resin (A), the dye contained in the ink composition, and the fabric.

[0076] The crosslinking agent can be appropriately selected from known crosslinking agents, and may be one that initiates the crosslinking reaction at room temperature or one that initiates the crosslinking reaction with heat. Examples of such crosslinking agents include self-crosslinking agents, compounds having multiple functional groups that react with unsaturated carboxylic acid components in their molecule, and metals having polyvalent coordination sites.

[0077] In order to achieve a better balance between the colorfastness and washability of the printed fabric and the texture of the printed fabric, it is preferable that the crosslinking agent contains an isocyanate group and / or an oxazoline group.

[0078] Examples of crosslinking agents containing isocyanate groups include water-dispersible (blocked) polyisocyanates. (Blocked) polyisocyanate refers to polyisocyanate and / or blocked polyisocyanate.

[0079] Examples of water-dispersible polyisocyanates include those obtained by dispersing a polyisocyanate, which has been given hydrophilicity by polyethylene oxide chains, in water with an anionic or nonionic dispersant.

[0080] Examples of polyisocyanates include diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate; and derivatives (modified products) of these diisocyanates, such as trimethylolpropane adducts, biuret compounds, and isocyanurates. These polyisocyanates may be used individually or in combination of two or more.

[0081] Water-dispersible blocked polyisocyanates are obtained by blocking the isocyanate groups of water-dispersible polyisocyanates with a blocking agent. Examples of blocking agents include diethyl malonate, ethyl acetoacetate, ε-caprolactam, butanone oxime, cyclohexanone oxime, 1,2,4-triazole, dimethyl-1,2,4-triazole, 3,5-dimethylpyrazole, and imidazole. These blocking agents may be used individually or in combination of two or more.

[0082] Commercially available crosslinking agents containing isocyanate groups can also be used. Examples of commercially available products include Fixer #100ECO, #104EA, #220, 70ECO, #70, #410, and #400 (all trade names, Murayama Chemical Research Institute Co., Ltd.); and Elastron® BN-11, BN-27, BN-69, and BN-77 (all trade names, Daiichi Kogyo Seiyaku Co., Ltd.).

[0083] Examples of crosslinking agents containing oxazoline groups include compounds having two or more oxazoline groups in their molecule. Examples of such oxazoline group-containing compounds include 2,2'-bis(2-oxazoline), 2,2'-methylene-bis(2-oxazoline), 2,2'-ethylene-bis(2-oxazoline), 2,2'-trimethylene-bis(2-oxazoline), 2,2'-tetramethylene-bis(2-oxazoline), 2,2'-hexamethylene-bis(2-oxazoline), and 2,2'-octamethylene-bis(2-oxazoline). Examples include 2,2'-ethylene-bis(4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(4,4'-dimethyl-2-oxazoline), bis(2-oxazolinylcyclohexane) sulfide, bis(2-oxazolinylnorbornane) sulfide, and oxazoline ring-containing polymers. These oxazoline group-containing compounds may be used individually or in combination of two or more.

[0084] Since it becomes possible to more firmly bond the polyester resin (A), the dye, and the fabric, and to obtain a printed product with better washability, a water-soluble oxazoline group-containing compound is preferred as the oxazoline group-containing compound.

[0085] Commercially available crosslinking agents containing oxazoline groups can also be used. Examples of such commercially available products include Epocross® K-2010, K-2020, K-2030, K-2035E, WS-300, WS-500, and WS-700 (all trade names, manufactured by Nippon Shokubai Co., Ltd.).

[0086] The crosslinking agent may be used alone or in combination of two or more types.

[0087] The crosslinking agent content (in terms of solids) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, particularly preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, and especially preferably 2.0% by mass or more, relative to the total amount of the pretreatment solution for textile printing. Furthermore, while there is no particular upper limit to the crosslinking agent content (in terms of solid content), it is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 2.5% by mass or less, relative to the total amount of the pretreatment solution for textile printing.

[0088] The mass ratio of polyester resin (A) to crosslinking agent (polyester resin / crosslinking agent) is preferably 0.1 to 20, more preferably 0.5 to 10, even more preferably 1 to 5, particularly preferably 1.2 to 3, and most particularly preferably 1.5 to 2.5. If the polyester resin (A) or crosslinking agent is in the form of an emulsion or the like, the mass ratio is calculated on a solid content basis.

[0089] 1.3 Water The pretreatment solution for textile printing according to this embodiment contains water. Water is evaporated and dispersed by drying after the pre-treatment solution for printing is applied to the fabric. Examples of suitable water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as ultrapure water from which ionic impurities have been removed as much as possible. Furthermore, water sterilized by ultraviolet irradiation or the addition of hydrogen peroxide is preferable because it can suppress the growth of mold and bacteria when the pre-treatment solution for printing is stored for a long period of time.

[0090] The water content is preferably 30% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more, relative to the total amount of the pretreatment solution for printing. There is no particular upper limit to the water content, but for example, it is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less, relative to the total amount of the pretreatment solution for printing. By keeping the water content within the above range, it is possible to suppress the increase in viscosity of the pre-treatment solution for textile printing, thereby improving the workability when applying the pre-treatment solution to the fabric and the drying speed after application.

[0091] 1.4 Organic Solvents The pretreatment solution for textile printing according to this embodiment may contain an organic solvent. Preferably, the organic solvent is a water-soluble organic solvent. "Water-soluble" means that the solubility in water at 20°C is greater than 10 g / 100 g of water.

[0092] Examples of organic solvents include esters, alkylene glycol ethers, cyclic esters, amides, alcohols, and polyhydric alcohols.

[0093] Esters include glycol monoacetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, methoxybutyl acetate, ethylene glycol diacetate, and diethylene glycol. Examples of glycol diesters include propyl diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, diethylene glycol acetate butyrate, diethylene glycol acetate propionate, diethylene glycol acetate butyrate, propylene glycol acetate propionate, propylene glycol acetate butyrate, dipropylene glycol acetate butyrate, and dipropylene glycol acetate propionate.

[0094] Examples of alkylene glycol ethers include alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers. Specific examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monobutyl ether. Examples include alkylene glycol monoalkyl ethers such as ethyl ether; and alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol methyl butyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and tripropylene glycol dimethyl ether.

[0095] Examples of cyclic esters include cyclic esters (lactones) such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, β-valerolactone, γ-valerolactone, β-hexanolactone, γ-hexanolactone, δ-hexanolactone, β-heptanolactone, γ-heptanolactone, δ-heptanolactone, ε-heptanolactone, γ-octanolactone, δ-octanolactone, ε-octanolactone, δ-nonalactone, ε-nonalactone, and ε-decanolactone, as well as compounds in which the hydrogen atoms of the methylene group adjacent to the carbonyl group are substituted with alkyl groups having 1 to 4 carbon atoms.

[0096] Examples of amides include cyclic amides and acyclic amides. Examples of acyclic amides include alkoxyalkyl amides.

[0097] Examples of cyclic amides include lactams. Examples of lactams include pyrrolidones such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone.

[0098] Examples of alkoxyalkylamides include 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-diethylpropionamide, 3-methoxy-N,N-methylethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-diethylpropionamide, 3-ethoxy-N,N-methylethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-diethylpropionamide, 3-n-butoxy-N,N-methylethylpropionamide, and 3-n-propoxy-N,N-dimethylpropionamide. Examples include propionamide, 3-n-propoxy-N,N-diethylpropionamide, 3-n-propoxy-N,N-methylethylpropionamide, 3-iso-propoxy-N,N-dimethylpropionamide, 3-iso-propoxy-N,N-diethylpropionamide, 3-iso-propoxy-N,N-methylethylpropionamide, 3-tert-butoxy-N,N-dimethylpropionamide, 3-tert-butoxy-N,N-diethylpropionamide, 3-tert-butoxy-N,N-methylethylpropionamide, N,N-dimethylisobutyrateamide, etc.

[0099] Examples of alcohols include compounds in which one hydrogen atom of an alkane is replaced by a hydroxyl group. The alkane preferably has 10 or fewer carbon atoms, more preferably 6 or fewer, and even more preferably 3 or fewer. The alkane has 1 or more carbon atoms, preferably 2 or more. The alkane may be linear or branched. Examples of alcohols include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, tert-butanol, iso-butanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol, 2-phenoxyethanol, benzyl alcohol, and phenoxypropanol.

[0100] Polyhydric alcohols are molecules that contain two or more hydroxyl groups. Polyhydric alcohols can be further classified into, for example, alkanediols and polyols.

[0101] Alkanediols include, for example, compounds in which an alkane is substituted with two hydroxyl groups. Examples of alkanediols include 1,2-alkanediols, which are a general term for compounds in which hydroxyl groups are substituted at the 1st and 2nd positions of an alkane, and other alkanediols other than 1,2-alkanediols.

[0102] Examples of 1,2-alkanediols include ethylene glycol, 1,2-propanediol (propylene glycol), 1,2-butanediol (1,2BD), 1,2-pentanediol (1,2PD), 1,2-hexanediol (1,2HD), 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 3-methyl-1,2-butanediol, 3-methyl-1,2-pentanediol, 4-methyl-1,2-pentanediol, and 3,4-dimethyl-1,2-pentanediol. Examples include hexanediol, 3-ethyl-1,2-pentanediol, 4-ethyl-1,2-pentanediol, 3-methyl-1,2-hexanediol, 4-methyl-1,2-hexanediol, 5-methyl-1,2-hexanediol, 3,4-dimethyl-1,2-hexanediol, 3,5-dimethyl-1,2-hexanediol, 4,5-dimethyl-1,2-hexanediol, 3-ethyl-1,2-hexanediol, 4-ethyl-1,2-hexanediol, and 3-ethyl-4-methyl-1,2-hexanediol.

[0103] Other examples of alkanediols include 1,3-propanediol, 1,3-butylene glycol (also known as 1,3-butanediol), 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol, 2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, 2-methylpentane-2,4-diol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, and 2-methyl-2-propyl-1,3-propanediol.

[0104] Examples of polyols include condensates formed by the intermolecular condensation of two or more alkanediol molecules via hydroxyl groups, and compounds having three or more hydroxyl groups.

[0105] Examples of condensates formed by the intermolecular condensation of two or more alkanediol molecules at their hydroxyl groups include dialkylene glycols such as diethylene glycol and dipropylene glycol, and trialkylene glycols such as triethylene glycol and tripropylene glycol.

[0106] Compounds having three or more hydroxyl groups are compounds with an alkane or polyether structure as their backbone and containing three or more hydroxyl groups. Examples of compounds having three or more hydroxyl groups include glycerin, trimethylolethane, trimethylolpropane, 1,2,5-hexanetriol, 1,2,6-hexanetriol, pentaerythritol, and polyoxypropylenetriol.

[0107] Organic solvents may be used individually or in combination of two or more types.

[0108] The pretreatment solution for textile printing according to this embodiment preferably contains one or more organic solvents selected from glycol-based solvents and glycerin derivatives. When such organic solvents are included, the color development of the printed material tends to be further improved.

[0109] Glycol-based solvents are solvents consisting of aliphatic or alicyclic compounds in which two hydroxyl groups are bonded to two different carbon atoms. Examples of glycol-based solvents include alkanediols and condensates obtained by intermolecular condensation of two or more alkanediol molecules via hydroxyl groups. Alkanediols are preferred, and 1,2-alkanediols are more preferred.

[0110] Examples of glycerin derivatives include polyoxyalkylene glyceryl ethers, which are glycerin obtained by addition or addition polymerization of at least one alkylene oxide. Examples of alkylene oxides include ethylene oxide, propylene oxide, and C4 alkylene oxides (1,2-butylene oxide, 2,3-butylene oxide, tetramethylene oxide, etc.).

[0111] Examples of polyoxyalkylene glyceryl ethers include polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, and polyoxyethylene polyoxypropylene glyceryl ether.

[0112] Polyoxyalkylene glyceryl ether may be a commercially available product, such as Sannix GP-250, GP-400, GP-600, GP-700, GP-1000, GP-1500, and GP-3000 (all product names manufactured by Sanyo Chemical Industries, Ltd.).

[0113] The content of the organic solvent is preferably 1 to 20% by mass, more preferably 2 to 18% by mass, even more preferably 3 to 15% by mass, and particularly preferably 5 to 10% by mass, relative to the total amount of the pretreatment solution for printing. It is also preferable to include one or more organic solvents selected from glycol-based solvents and glycerin derivatives within the above range.

[0114] 1.5 Viscosity modifier The pretreatment solution for textile printing according to this embodiment may contain a viscosity modifier. The inclusion of a viscosity modifier tends to further improve color development.

[0115] Examples of viscosity modifiers include inorganic thickeners and organic thickeners.

[0116] Examples of inorganic thickeners include inorganic compounds such as silica (SiO2), alumina, and titania, as well as clay minerals such as bentonite and montmorillonite. Among these, silica powder, hydrophobically treated silica powder, or mixtures thereof are preferred.

[0117] Specifically, examples include silica fine powder pulverized by a dry method [e.g., manufactured by Nippon Aerosil Co., Ltd., product name: Aerosil 300, etc.], fine powder obtained by modifying this silica fine powder with trimethyldisilazane [e.g., manufactured by Nippon Aerosil Co., Ltd., product name: Aerosil RX300, etc.], and fine powder obtained by modifying the above silica fine powder with polydimethylsiloxane [e.g., manufactured by Nippon Aerosil Co., Ltd., product name: Aerosil RY300, etc.]. From the viewpoint of imparting viscosity and pseudoplasticity, the average particle size of the inorganic thickener is preferably 5 to 50 μm, and more preferably 5 to 12 μm.

[0118] Examples of organic thickeners include polysaccharides, water-soluble thickening resins, and modified versions thereof.

[0119] Examples of polysaccharides include xanthan gum (Kelzan), welan gum, ramzan gum, succinoglycans, guar gum, locust bean gum, pullulan, dextran, dextrin, tragacanth gum, tara gum, gadigan gum, arabinogalactan gum, gum arabic, quisseed gum and its derivatives, as well as pectin, starch, carrageenan, agar, alginic acid, gelatin, casein, glucomannan, carrageenan, benzylidene sorbitol and benzylidene xylitol, leozhan, dieutan gum, and the like.

[0120] Examples of water-soluble thickening resins include cellulosic compounds such as carboxyethylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, and viscose; vinyl compounds consisting of water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone; alkyd resins, acrylic resins, styrene-maleic acid copolymers, cellulose derivatives, polyvinylpyrrolidone, polyvinyl alcohol, poly(meth)acrylic acid compounds, polyether-modified urethane compounds, hydrophobic-modified polyoxyethylene polyurethane copolymers, and other polyurethane compounds; polyamide compounds such as polyamide wax amine salts; and urea compounds such as urethane-urea compounds. Examples include alkyl alginates, ester compounds such as alkyl esters of methacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, polyacrylamide, polyN-vinylacetamide, N-vinylacetamide resin and derivatives thereof, as well as urethane-urea thickeners and amide-urea thickeners.

[0121] As a viscosity modifier, a urethane-based thickener is preferred from the viewpoint of having superior color development properties. Commercially available urethane-based thickeners may be used, such as SN Thickener 621TF, 660T, and 665T (all product names of Sunopco Corporation).

[0122] The viscosity modifier content is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, even more preferably 0.1 to 1% by mass, and particularly preferably 0.1 to 0.5% by mass, relative to the total amount of the pretreatment solution for printing.

[0123] 1.6 Other Ingredients The pretreatment solution for textile printing according to this embodiment may contain various additives such as surfactants, solubilizers, pH adjusters, antioxidants, preservatives, fungicides, corrosion inhibitors, and chelating agents. These additives may be used individually or in combination of two or more.

[0124] The additive content may be, for example, 0.01 to 5.0% by mass of the total amount of the pre-treatment solution for printing.

[0125] 1.7 Method for producing pre-treatment solution for textile printing Pre-treatment solutions for textile printing can be prepared by mixing the components in any order and removing impurities and foreign matter by filtration or other methods as needed. Methods for mixing the components include sequentially adding each component to a container equipped with a stirring device such as a mechanical stirrer or magnetic stirrer, and then stirring and mixing them. Filtration methods include centrifugal filtration and filter filtration.

[0126] 1.8 Physical Properties The viscosity of the pre-treatment solution for textile printing at 20°C is preferably between 1.5 mPa·s and 100 mPa·s. By setting the viscosity of the pre-treatment solution for textile printing within the above range, the coating properties, such as the ease with which the pre-treatment solution spreads when applied to the fabric, can be improved. The viscosity of the pre-treatment solution for textile printing is measured, for example, using a viscoelasticity tester MCR-300 (Pysica). Specifically, it can be measured by adjusting the temperature of the pre-treatment solution to 20°C and reading the shear viscosity (mPa·s) at a shear rate of 200 (1 / s).

[0127] The surface tension of the pre-treatment solution for textile printing at 25°C is preferably between 30 mN / m and 50 mN / m. By setting the surface tension of the pre-treatment solution for textile printing at 25°C within the above range, appropriate wettability and penetration to the fabric are achieved. Furthermore, since the pre-treatment solution for textile printing is more easily absorbed uniformly into the fabric, it is possible to suppress the occurrence of differences in the amount of adhesion, i.e., uneven coating, that occurs when applying the pre-treatment solution for textile printing. The surface tension of the pre-treatment solution for textile printing can be measured, for example, using an automatic surface tension meter CBVP-Z (Kyowa Interface Science Co., Ltd.). Specifically, it can be measured by reading the surface tension when a platinum plate is wetted with the pre-treatment solution for textile printing in an environment of 25°C.

[0128] 2. Printing Method A printing method according to one embodiment of the present invention includes a coating step of applying the above-mentioned pre-treatment liquid for printing to a fabric, a drying step of drying the fabric to which the pre-treatment liquid for printing has been applied by heating, a recording step of applying an ink composition containing a disperse dye and water to an intermediate transfer medium and recording it, and a transfer step of transferring the ink composition applied to the intermediate transfer medium to the fabric to which the pre-treatment liquid for printing has been applied.

[0129] The printing method according to this embodiment uses the above-described pretreatment solution for printing, and makes it possible to achieve both the resistance to discoloration and fading of the printed material, washability, and the texture of the printed material.

[0130] The following describes each step of the printing method according to this embodiment.

[0131] 2.1 Coating process The printing method according to this embodiment includes a coating step of applying the above-mentioned pre-treatment solution for printing to the fabric.

[0132] Methods for applying the pre-treatment solution for printing to the fabric include, for example, an immersion coating method in which the fabric is immersed in the pre-treatment solution; a roller coating method in which the pre-treatment solution is applied using a mangle roller or roll coater; a spray coating method in which the pre-treatment solution is sprayed using a spray device; and an inkjet coating method in which the pre-treatment solution is sprayed using an inkjet method. These coating methods may be used individually to apply the pre-treatment solution to the fabric, or two or more methods may be combined to apply the pre-treatment solution to the fabric. In this embodiment, the degree of design freedom for the amount of pre-treatment solution applied to the fabric is increased, problems during application are less likely to occur, and the pre-treatment solution can be uniformly applied to the fabric. Therefore, it is preferable to apply the pre-treatment solution to the fabric using a roller coating method with rollers such as mangle rollers or roll coaters.

[0133] The amount of pre-treatment solution for printing applied to the fabric is not particularly limited, but is generally between 0.1 and 10 g / cm³. 2 Preferably, 0.5 to 8 g / cm³ 2 More preferably, 1-5 g / cm³ 2 More preferably, 2-3 g / cm³ 2 This is particularly preferable. By setting the amount of pre-treatment solution applied to the fabric within the above range, the pre-treatment solution can be applied more uniformly to the fabric, which tends to further improve color development.

[0134] The form of the fabric is not particularly limited and includes, for example, cloth, clothing, and other fashion accessories. Cloth includes woven fabrics, knitted fabrics, and nonwoven fabrics. Clothing and other fashion accessories include finished items such as T-shirts, handkerchiefs, scarves, towels, tote bags, cloth bags, curtains, sheets, bedspreads, wallpaper and other furniture, as well as fabrics before and after cutting as components before sewing. These can take the form of long rolls, cut to a predetermined size, or in the shape of finished products.

[0135] The materials that make up the fabric are not particularly limited and include, for example, natural fibers such as cotton, linen, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane; and biodegradable fibers such as polylactic acid. Blends of these fibers are also acceptable.

[0136] As for the fabric, a fabric that has been pre-colored with a dye may be used. Examples of dyes used to pre-color the fabric include water-soluble dyes such as acid dyes and basic dyes; disperse dyes used in combination with a dispersant; reactive dyes; and solvent dyes.

[0137] 2.2 Drying process The printing method according to this embodiment includes a drying step of drying the fabric to which the above-described pretreatment liquid for printing is attached by heating.

[0138] Examples of the heating method include a heat press method, an atmospheric pressure steam method, a high pressure steam method, and a thermofix method. Examples of the heat source for heating include infrared rays (lamps). Moreover, the heating temperature is preferably, for example, 210 °C or lower, more preferably 200 °C or lower, and even more preferably 190 °C or lower. Thereby, even if the fabric is pre-colored with a dye, sublimation of the dye due to heat drying can be suppressed, and fading of the fabric base color can be suppressed. The lower limit of the heating temperature is such that a medium such as moisture contained in the pretreatment liquid for printing may volatilize, and it is preferably 100 °C or higher, more preferably 120 °C or higher, and even more preferably 140 °C or higher. Here, the heating temperature refers to the average temperature in the region where the recording on the fabric surface is made. The drying time is preferably 10 seconds or more and 10 minutes or less, more preferably 20 seconds or more and 5.0 minutes or less, and even more preferably 20 seconds or more and 3.0 minutes or less.

[0139] Moreover, the pressure when heating under pressure is preferably 0.05 to 5 N / cm 2 is more preferably 0.1 to 1 N / cm 2 is even more preferably 0.15 to 0.5 N / cm 2 is even more preferable.

[0140] 2.3 Recording step The printing method according to this embodiment includes a recording step of discharging an ink composition containing a disperse dye and water from an inkjet head and attaching it to an intermediate transfer medium for recording.

[0141] The amount of the ink composition attached to the intermediate transfer medium is not particularly limited, but for example, 3 to 20 mg / inch 2 is preferably 5 to 17 mg / inch 2 is more preferably 8 to 15 mg / inch 2That is even more preferable.

[0142] As an intermediate transfer medium, for example, paper such as plain paper and a recording medium provided with an ink-receiving layer can be used. The above-mentioned recording medium provided with an ink-receiving layer is referred to as, for example, inkjet-specific paper and coated paper. Among these, paper provided with an ink-receiving layer containing inorganic particles such as silica is more preferable. This makes it possible to obtain an intermediate recording in which bleeding and other issues are suppressed on the recording surface during the drying process of the ink composition applied to the intermediate transfer medium. Furthermore, with such a medium, it is easier to retain the disperse dye on the surface of the recording surface, and the sublimation of the disperse dye tends to be performed more efficiently in the subsequent transfer process.

[0143] 2.3.1 Ink composition The ink composition used in the recording process contains a disperse dye and water. The components of the ink composition are described below. Preferably, the ink composition is an inkjet ink composition that is ejected from an inkjet head by an inkjet method and applied to a recording medium.

[0144] 2.3.1.1 Disperse dyes The ink composition contains a disperse dye as a dye. Disperse dyes are colorants that typically form particulate matter and are dispersed in a dispersion medium by a dispersant. Disperse dyes are also typically nonionic dyes that have hydrophilic groups and moderately polar groups. Disperse dyes may be used individually or in combination of two or more types.

[0145] Examples of disperse dyes include CI Disperse Yellow, CI Disperse Red, CI Disperse Blue, CI Disperse Orange, CI Disperse Violet, CI Disperse Green, CI Disperse Brown, and CI Disperse Black.

[0146] Among these, sublimation dyes are preferred as dispersants. Here, "sublimation dyes" refer to dyes that have the property of sublimating when heated. Specifically, such sublimation dyes include CI Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, and 86; CI Disperse Orange 1, 1:1, 5, 20, 25, 25:1, 33, 56, and 76; CI Disperse Brown 2; CI Disperse Red 11, 50, 53, 55, 55:1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190:1, and 20 Examples include 7, 239, and 240; CI Bat Red 41; CI Disperse Violet 8, 17, 23, 27, 28, 29, 36, and 57; CI Disperse Blue 14, 19, 26, 26:1, 35, 55, 56, 58, 64, 64:1, 72, 72:1, 81, 81:1, 91, 95, 108, 131, 141, 145, and 359; CI Solvent Blue 36, 63, 105, and 111, etc.

[0147] In this embodiment, cyan dyes, red dyes, and yellow dyes are preferred because they tend to yield better dyeability and prints with sufficient color development on fabrics to which the above-mentioned pre-treatment solution for printing has been applied. Furthermore, CI Disperse Blue 359 is more preferred as the cyan dye, CI Disperse Red 60 is more preferred as the red dye, and CI Disperse Yellow 54 is more preferred as the yellow dye, as these yield even better dyeability and prints with sufficient color development.

[0148] The content of the disperse dye is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, even more preferably 2 to 8% by mass, and particularly preferably 3 to 6% by mass, relative to the total amount of the ink composition.

[0149] 2.3.1.2 Water The ink composition contains water. The water is described in the same way as in the pre-treatment solution for textile printing described above.

[0150] The water content is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and even more preferably 50 to 75% by mass, relative to the total amount of the ink composition.

[0151] 2.3.1.3 Dispersant The ink composition may contain a dispersant. When an ink composition contains a dispersant, the dispersibility of the disperse dye tends to be superior, and the ink composition tends to have superior clogging resistance.

[0152] Examples of dispersants include sodium naphthalene sulfonate-formaldehyde condensate and resins. Sodium naphthalene sulfonate-formaldehyde condensate is a compound obtained by formalin condensation of a sulfonate having a naphthalene ring in its molecule, or a salt thereof. Dispersants may be used individually or in combination of two or more.

[0153] Because they have better dispersibility, it is preferable that the dispersant contains a resin. Examples of resins include urethane resins, styrene-acrylic resins, acrylic resins, fluorene resins, polyolefin resins, rosin-modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and ethylene vinyl acetate resins. Among these, urethane resins and styrene-acrylic resins are preferred, and styrene-acrylic resins are more preferred, due to their excellent resistance to clogging.

[0154] The urethane resin is not particularly limited as long as it has urethane bonds in its molecule. Examples of urethane resins include polyether-type urethane resins containing ether bonds in the main chain in addition to urethane bonds, polyester-type urethane resins containing ester bonds in the main chain, and polycarbonate-type urethane resins containing carbonate bonds in the main chain. The urethane resin may be used alone or in combination of two or more types.

[0155] Commercially available urethane resins can also be used. Examples of commercially available products include Takelac® W6110 (product name) from Mitsui Chemicals, Inc., Acrit® WBR-022U (product name) from Taisei Fine Chemical Co., Ltd., Permarin® UX-368T (product name), Euprene® UXA-307 (product name), and U-Coat® UWS-145 (product name) from Sanyo Chemical Industries, Ltd., and Solusbarth® 47000 (product name) from Lubrizol.

[0156] Examples of styrene-acrylic resins include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene-α-methylstyrene-acrylic acid copolymers, and styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymers. These copolymers may be in any of the following forms: random copolymers, block copolymers, alternating copolymers, and graft copolymers.

[0157] Commercially available styrene-acrylic resins can also be used. Examples of commercially available products include Joncryl® 67 (trade name) manufactured by BASF Japan Ltd., and Solusbarth® 43000 (trade name) manufactured by Lubrizol.

[0158] The dispersant content is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, even more preferably 2 to 8% by mass, and particularly preferably 3 to 6% by mass, relative to the total amount of the ink composition. Furthermore, the ratio of the dispersant content to the dispersant content is preferably 0.5 to 1.5, more preferably 0.7 to 1.2, and even more preferably 0.9 to 1.1.

[0159] 2.3.1.4 Surfactants The ink composition may contain a surfactant.

[0160] Examples of surfactants include acetylene glycol-based surfactants, fluorine-based surfactants, and silicone-based surfactants. Surfactants may be used individually or in combination of two or more types.

[0161] Examples of acetylene glycol-based surfactants include 2,4,7,9-tetramethyl-5-decine-4,7-diol and its alkylene oxide adduct, and 2,4-dimethyl-5-decine-4-ol and its alkylene oxide adduct. Commercially available acetylene glycol-based surfactants can also be used. Examples of commercially available products include the Orfin® 104 series (product name) and E series (product name) manufactured by Nisshin Chemical Industry Co., Ltd., and the Surfinol® series (product name) manufactured by Air Products and Chemicals Inc.

[0162] Examples of fluorinated surfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphate esters, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkylamine oxide compounds. Commercially available fluorine-based surfactants can also be used. Examples of commercially available products include S-144 (product name) and S-145 (product name) manufactured by Asahi Glass Co., Ltd.

[0163] Examples of silicone-based surfactants include polysiloxane compounds and polyether-modified organosiloxanes. Commercially available silicone-based surfactants can also be used. Examples of commercially available products include BYK® series 306, 307, 333, 341, 345, 346, 347, 348, and 349 (all product names) manufactured by BYK Chemie Japan Co., Ltd.

[0164] The surfactant content is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, even more preferably 0.1 to 3% by mass, and particularly preferably 0.3 to 1% by mass, relative to the total amount of the ink composition.

[0165] 2.3.1.5 Organic Solvents The ink composition may contain an organic solvent. The organic solvent is described in the same way as described above for the pretreatment solution for textile printing.

[0166] The content of the organic solvent is preferably 5 to 40% by mass, more preferably 8 to 35% by mass, even more preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass, based on the total amount of the ink composition.

[0167] 2.3.1.6 Other ingredients The ink composition may contain various additives, such as solubilizers, viscosity modifiers, pH adjusters, antioxidants, preservatives, fungicides, corrosion inhibitors, and chelating agents for capturing metal ions that may affect dispersion. Additives may be used individually or in combination of two or more.

[0168] Examples of preservatives include sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, and 1,2-dibenzinthiazolin-3-one. Commercially available preservatives can also be used. Examples of commercially available preservatives include the Proxel® series from Lonza Japan, specifically CRL, BND, GXL, XL-2, and TN (all are trade names). Preservatives may be used individually or in combination of two or more types.

[0169] The additive content may be, for example, 0.01 to 5.0% by mass of each additive relative to the total amount of the ink composition.

[0170] 2.3.1.7 Method for producing ink composition The ink composition can be prepared in the same manner as the pretreatment solution for printing described above. Alternatively, in order to better disperse the disperse dye in the ink composition, a dye dispersion may be prepared in advance, and the ink composition may be prepared using the dye dispersion instead of the disperse dye. The dye dispersion can be obtained, for example, by mixing a disperse dye, water, and a dispersant in any order and dispersing them using a paint shaker or the like.

[0171] 2.3.1.8 Physical Properties From the viewpoint of ensuring proper wetting and spreading properties on fabric, the ink composition preferably has a surface tension of 40 mN / m or less, preferably 38 mN / m or less, more preferably 35 mN / m or less, and even more preferably 30 mN / m or less at 25°C.

[0172] The ink composition preferably has a viscosity of 1.5 mPa·s to 15 mPa·s at 20°C, more preferably 1.5 mPa·s to 7 mPa·s, and even more preferably 1.5 mPa·s to 5.5 mPa·s.

[0173] 2.4 Transfer process The printing method according to this embodiment includes a transfer step of transferring the above-mentioned ink composition attached to an intermediate transfer medium to a fabric to which a pre-treatment solution for printing has been attached.

[0174] The transfer process involves heating the surface of the intermediate transfer medium to which the ink composition is attached, and the surface of the fabric to which the printing pretreatment solution is attached, with these surfaces facing each other, thereby transferring the disperse dye contained in the ink composition to the fabric to which the printing pretreatment solution is attached. As a result, a printed product is obtained, which is the fabric to which the disperse dye is transferred and the ink composition is attached.

[0175] In this process, the intermediate transfer medium to which the ink composition has been applied should be heated while facing the fabric to which the pre-treatment solution for printing has been applied. In this process, it is more preferable to heat the intermediate transfer medium and the fabric to which the pre-treatment solution for printing has been applied while they are in close contact. This allows, for example, a clearer image to be recorded on the fabric to which the pre-treatment solution for printing has been applied, i.e., dyed.

[0176] Examples of heating methods include steaming with steam, heat pressing with dry heat, thermosol, HT steamer with superheated steam, and HP steamer with pressurized steam. The fabric to which the ink composition has been applied may be heat-treated immediately, or it may be heat-treated after a predetermined time has elapsed. Dry heat is preferred as the heating method because it yields an impression with sufficient color development, resistance to discoloration and fading, and washability.

[0177] The heating temperature is preferably 160-220°C, more preferably 170-210°C, and particularly preferably 180-190°C. When the heating temperature is within this range, the energy required for transfer can be reduced, resulting in improved productivity of the printed material. Furthermore, the color development of the printed material tends to be superior.

[0178] The heating time, depending on the heating temperature, is preferably 30 to 120 seconds, and more preferably 40 to 90 seconds. Heating within this range reduces the energy required for transfer, resulting in improved productivity of the printed material. Furthermore, it tends to result in superior color development of the printed material.

[0179] Furthermore, the pressure used when heating under pressure is 10-50 g / cm². 2 Preferably, 15-40 g / cm³ 2 More preferably, 20-30 g / cm³ 2 That is even more preferable.

[0180] The amount of ink composition that adheres to the fabric through transfer is, for example, 1.5 to 6.0 mg / cm² per unit area of ​​the fabric. 2It is preferable that the amount of ink composition adhered is within the above range, which improves the color development of images formed by printing, ensures that the ink adheres to the fabric dries properly, and tends to reduce the occurrence of blurring of images.

[0181] 2.5 Other processes The printing method according to this embodiment may include, if necessary, steps such as preheating the fabric to which the printing pretreatment solution has been applied, washing the fabric to which the printing pretreatment solution has been applied, and washing the printed object.

[0182] 2.6 Inkjet Recording Devices The inkjet recording apparatus that can be used in the printing method according to this embodiment is not particularly limited as long as it has at least an ink container for containing an ink composition and an inkjet head connected thereto, and can eject the ink composition from the inkjet head to form an image on a recording medium such as an intermediate transfer medium. In addition, either a serial type or a line type inkjet recording apparatus can be used. These types of inkjet recording apparatuses are equipped with an inkjet head, and while changing the relative positional relationship between the recording medium and the inkjet head, droplets of the ink composition are ejected from the nozzle holes of the inkjet head intermittently and in a predetermined volume at predetermined timings. This makes it possible to adhere the ink composition to the recording medium and form a predetermined transfer image.

[0183] In general, in serial inkjet recording devices, the transport direction of the recording medium and the reciprocating direction of the inkjet head intersect, and the relative positional relationship between the recording medium and the inkjet head is changed by the combination of the reciprocating motion of the inkjet head and the transport motion of the recording medium. In this case, the inkjet head generally has multiple nozzle holes, and rows of nozzle holes, or nozzle rows, are formed along the transport direction of the recording medium. In addition, depending on the type and number of ink compositions, multiple nozzle rows may be formed on the inkjet head.

[0184] Furthermore, in line-type inkjet recording devices, the inkjet head does not perform a reciprocating motion; instead, the relative positional relationship between the recording medium and the inkjet head is changed by the transport of the recording medium. In this case as well, the inkjet head generally has multiple nozzle holes, and a row of nozzles is formed in a direction intersecting the transport direction of the recording medium.

[0185] 3. Examples The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" below refers to mass.

[0186] 3.1 Preparation of pre-treatment solution for printing Each component was placed in a mixing tank to obtain the composition shown in Table 1 (Figure 1), mixed and stirred, and then filtered through a 5 μm membrane filter to obtain the pre-treatment solution for printing for each example. Note that the numerical values ​​for the amount of each component in Table 1 represent mass percent. The amounts for polyester resin and crosslinking agent are shown on a solids basis. Water was added so that the total mass of the composition was 100% by mass.

[0187] Further explanation is provided regarding the information in Table 1. [Polyester resin] Polyester resins A to M were obtained by the following procedure.

[0188] (Method of manufacturing polyester resin A) In a reaction vessel equipped with a condenser, thermometer, stirrer, and nitrogen inlet, 422 parts by weight of diethylene glycol, 27 parts by weight of trimethylolpropane, 348 parts by weight of terephthalic acid, 348 parts by weight of isophthalic acid, and 6 parts by weight of phthalic anhydride, along with tetrabutoxytitanate as a condensation catalyst at a concentration of 1000 ppm relative to the total weight of the raw materials, were added. The reaction was carried out at 200°C under a nitrogen stream for 6 hours while distilling off the water produced. The reaction was further carried out under reduced pressure of 0.5 to 2.5 kPa, and the reactants were removed from the reaction vessel to obtain polyester resin A.

[0189] (Manufacturing method for polyester resins B-M) In a reaction vessel equipped with a condenser, stirrer, and nitrogen inlet, the alcohol and carboxylic acid components listed in Table 2 (Figure 2) were charged, and the reaction was carried out in the same manner as the method for producing polyester resin A described above, to obtain polyester resins B to M. The physical properties of each polyester resin are shown in Table 2. However, the excess ethylene glycol was removed from the reaction system by distillation. The composition ratios of the polyester resins shown in Table 2 are the composition ratios of the final composition. The composition of the polyester resins was measured by determining the molar ratio of the constituent polyhydric alcohol and polyhydric carboxylic acid components using a 400 MHz 1H-nuclear magnetic resonance spectrometer [BRUKER, "AVANCE III HD400N"]. Deuterated chloroform was used as the solvent.

[0190] [Crosslinking agent] • Isocyanate-based crosslinking agent (Fixer #220, trade name, Murayama Chemical Research Institute Co., Ltd.) • Oxazoline-based crosslinking agent (Epocross K-2035E, product name, Nippon Shokubai Co., Ltd.)

[0191] [Organic solvents] • 1,2-Hexanediol (glycol-based solvent) • Sannix GP-250 (Polyoxyalkylene glyceryl ether, product name, Sanyo Chemical Industries, Ltd.)

[0192] [Viscosity modifier] • SN Thickener 621TF (urethane-based thickener, product name, Sunopco Co., Ltd.)

[0193] 3.2 Preparation of the printed material The pre-treatment solution for printing obtained in each of the above examples was applied at a coating rate of 2.0 to 3.0 g / cm². 2 Each of the colors was applied to a white cotton T-shirt [Printstar, "5.6 oz CVT Heavyweight T-shirt"] using a paint roller designed for water-based paints. Then, a flat sublimation transfer press [Hashima Corporation, "HSP-5400"] was used at a temperature of 185°C and a pressure of 0.2 N / cm². 2 The fabric was then dried under conditions of 30 seconds to produce a cloth coated with polyester resin.

[0194] Sublimation cyan ink [Seiko Epson Corporation "SC23C"] was filled into the cartridge of an inkjet printer [Seiko Epson Corporation "EW-052A"]. ​​Then, an image with a 96dpi x 96dpi filled pattern was printed twice onto sublimation transfer paper [Seiko Epson Corporation "DS Transfer General Purpose"] to create ink-coated transfer paper.

[0195] The surface on which the image of the transfer paper obtained above is formed is then transferred to the surface of the polyester resin-coated fabric obtained above using a flat sublimation transfer press [HSP-5400 manufactured by Hashima Co., Ltd.] at a temperature of 185°C and a pressure of 25 g / cm². 2 The fabric was then heat-transferred under conditions of 60 seconds to obtain a printed object, which was a piece of cloth to which cyan ink for sublimation transfer had been applied.

[0196] 3.3 Evaluation Method 3.3.1 Color development The recording surface of each obtained print was measured using a Konica Minolta FD-7 spectrodensitometer under the conditions of a D65 light source and a field of view of 2 degrees, and the OD value was measured. The color development was evaluated based on the following evaluation criteria. If the evaluation result is B or higher, it can be said that the color development is excellent. (Evaluation Criteria) A: The OD of the recording surface is 1.20 or higher. B: The OD of the recording surface is 1.10 or greater and less than 1.20. C: The OD of the recording surface is 1.00 or greater and less than 1.10. D: The OD of the recording surface is less than 1.00.

[0197] 3.3.2 Discoloration The discoloration resistance was evaluated by comparing the OD value of the printed material immediately after printing with the OD value of the printed material after being left for 3 days. A result of B or higher indicates excellent discoloration resistance. (Evaluation Criteria) A: The rate of change in the OD value was less than 1%. B: The rate of change in the OD value was between 1% and less than 2%. The rate of change in the C:OD value was between 2% and less than 3%. The rate of change in the D:OD value was 3% or more.

[0198] 3.3.3 Washability The washability of the obtained prints was tested according to the A-2 method of JIS L0844 (Test method for color fastness to washing). Specifically, each print was washed in a household washing machine (ZABOON (product name), manufactured by Toshiba Corporation) using a general household laundry detergent (fluorescent whitening agent-free), and the discoloration of the prints was judged after rinsing, spinning, and drying. Discoloration was evaluated according to the JIS L0804:2004 (ISO 105-C10(B2)) discoloration grayscale, and the degree of fading was assessed according to the following evaluation criteria. If the evaluation result is B or higher, it can be said that the wash resistance is excellent. (Evaluation Criteria) A: The wash fastness is rated 5 or higher. B: Wash fastness is between level 4 and level 5. C: Wash fastness is between grade 3 and grade 4. D: Wash fastness is between grade 2 and grade 3.

[0199] 3.3.4 Texture The texture of the obtained printed materials was evaluated through a sensory test. Specifically, five random judges evaluated the obtained printed materials on whether they were "indistinguishable from the original feel of the fabric" or "stiff and rough, losing the original feel of the fabric." The texture was then evaluated based on these results and the following evaluation criteria. A result of B or higher indicates excellent texture. (Evaluation Criteria) A: Five judges responded that the fabric had "no inferiority to the original texture of the material." B: Four judges responded that the fabric had "no inferiority to the original texture of the material." C: Three judges responded that the fabric had "no inferiority to the original texture of the cloth." D: Two or fewer judges responded that the fabric had "no inferiority to the original texture of the cloth."

[0200] 3.4 Evaluation Results The evaluation results are shown in Table 1. In each example relating to the pre-treatment solution for textile printing, which comprises a polyester resin (A) obtained by polycondensation of an alcohol component and a carboxylic acid component, a crosslinking agent, and water, wherein the carboxylic acid component contains phthalic acid, the acid value of the polyester resin (A) is 5 to 40 mg KOH / g, the aromatic ring concentration of the polyester resin (A) is 4.20 to 5.20 mol / kg, and the glass transition temperature of the polyester resin (A) is 0 to 40°C, the printed fabric exhibited good colorfastness, texture, and washability.

[0201] In contrast, the pre-treatment solutions for printing used in each comparative example that did not satisfy the above configuration were inferior in at least one of the following aspects of the printed material: discoloration, texture, and washability.

[0202] The following conclusions can be drawn from the embodiments described above.

[0203] One embodiment of a pretreatment solution for textile printing is: A pre-treatment solution for textile printing comprising a polyester resin (A) obtained by polycondensation of an alcohol component and a carboxylic acid component, a crosslinking agent, and water, The carboxylic acid component contains phthalic acid, the acid value of the polyester resin (A) is 5 to 40 mg KOH / g, the aromatic ring concentration of the polyester resin (A) is 4.20 to 5.20 mol / kg, and the glass transition temperature of the polyester resin (A) is 0 to 40°C.

[0204] In one embodiment of the above-mentioned pre-treatment solution for textile printing, The peak top molecular weight of the polyester resin (A) may be 3,000 to 20,000.

[0205] In any embodiment of the above-described pretreatment solution for textile printing, The hydroxyl value of the polyester resin (A) may be 0 to 40 mg KOH / g.

[0206] In any embodiment of the above-described pretreatment solution for textile printing, The carboxylic acid component may further contain isophthalic acid, and the molar ratio of phthalic acid to isophthalic acid (phthalic acid:isophthalic acid) may be 1:99 to 99:1.

[0207] In any embodiment of the above-described pretreatment solution for textile printing, The organic solvent may include one or more selected from glycol-based solvents and glycerin derivatives.

[0208] In any embodiment of the above-described pretreatment solution for textile printing, It may contain viscosity modifiers.

[0209] In any embodiment of the above-described pretreatment solution for textile printing, The content of the polyester resin (A) may be 1% by mass or more and 20% by mass or less in terms of solid content relative to the total amount of the pretreatment solution for printing.

[0210] One aspect of the printing method is: A coating step of applying a pre-treatment solution for printing, according to any of the above embodiments, to a fabric, A drying step in which the fabric to which the pre-treatment solution for printing has been applied is dried by heating, A recording process in which an ink composition containing a disperse dye and water is ejected from an inkjet head and deposited onto an intermediate transfer medium for recording, The process includes a transfer step of transferring the ink composition adhering to the intermediate transfer medium to the fabric to which the pre-treatment solution for printing has been applied.

[0211] The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes configurations that are substantially identical to the configurations described in the embodiments, for example, configurations that have the same function, method and result, or configurations that have the same purpose and effect. The present invention also includes configurations in which non-essential parts of the configurations described in the embodiments are replaced. Furthermore, the present invention includes configurations that produce the same effects or achieve the same purpose as the configurations described in the embodiments. Furthermore, the present invention includes configurations that add known technology to the configurations described in the embodiments.

Claims

1. A pre-treatment solution for textile printing comprising a polyester resin (A) obtained by polycondensation of an alcohol component and a carboxylic acid component, a crosslinking agent, and water, A pretreatment solution for textile printing, wherein the carboxylic acid component contains phthalic acid, the acid value of the polyester resin (A) is 5 to 40 mg KOH / g, the aromatic ring concentration of the polyester resin (A) is 4.20 to 5.20 mol / kg, and the glass transition temperature of the polyester resin (A) is 0 to 40°C.

2. The pretreatment solution for textile printing according to claim 1, wherein the peak top molecular weight of the polyester resin (A) is 3,000 to 20,000.

3. The pretreatment solution for textile printing according to claim 1 or claim 2, wherein the hydroxyl value of the polyester resin (A) is 0 to 40 mg KOH / g.

4. The pretreatment solution for textile printing according to claim 1 or claim 2, wherein the carboxylic acid component further contains isophthalic acid, and the molar ratio of phthalic acid to isophthalic acid (phthalic acid:isophthalic acid) is 1:99 to 99:

1.

5. A pretreatment solution for textile printing according to claim 1 or claim 2, comprising one or more selected from glycol-based solvents and glycerin derivatives as an organic solvent.

6. A pretreatment solution for textile printing according to claim 1 or claim 2, comprising a viscosity modifier.

7. The pre-treatment solution for textile printing according to claim 1 or claim 2, wherein the content of the polyester resin (A) is 1% by mass or more and 20% by mass or less in terms of solid content relative to the total amount of the pre-treatment solution for textile printing.

8. A coating step of applying the pre-treatment solution for printing described in claim 1 or claim 2 to a fabric, A drying step in which the fabric to which the pre-treatment solution for printing has been applied is dried by heating, A recording process in which an ink composition containing a disperse dye and water is ejected from an inkjet head and deposited onto an intermediate transfer medium for recording, A printing method comprising a transfer step of transferring the ink composition adhering to the intermediate transfer medium to the fabric to which the printing pretreatment solution has been applied.

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