Fabric pretreatment agent, printing method, and printed fabric

Abstract

To provide fabric pre-treatment agent, a textile printing method, and a textile printed fabric which can strike a balance between the color development and the feeling and also can suppress the bleed-out of a dye.SOLUTION: A fabric pre-treatment agent is used in textile printing by the sublimation transfer technique and comprises a solvent having an I / O value of 1.5 or more, the I / O value being the ratio of an inorganic value to an organic value, and an aromatic heterocyclic compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a fabric pretreatment agent, a textile printing method, and a printed fabric, and more particularly to a fabric pretreatment agent that can achieve both good color development and texture and can also suppress dye bleeding out. [Background technology]

[0002] A sublimation transfer method has been known in the past, in which a sublimation dye printed on transfer paper is thermally transferred onto polyester fabric. However, when used on fabrics other than polyester, such as cotton, the sublimation dye is not fixed properly due to the difference in polarity between the sublimation dye and the fabric, resulting in insufficient print density. To address this problem, a method has recently been proposed in which a resin such as a polyester resin is applied to the cotton fabric and then the applied resin is dyed, but achieving both color density and texture is a major problem.

[0003] For example, Patent Document 1 discloses a technique in which a cellulose fiber structure is treated with an acid chloride and an N-heterocyclic compound to prevent deterioration of the cellulose fiber, and then chemically modified by heat treatment or dry heat treatment, followed by printing with a dye. However, the acid chlorides used as pretreatment agents were benzoyl chloride, parachlorobenzene chloride, p-toluenesulfonyl chloride, benzenesulfonyl chloride, etc., and the ratio of inorganic to organic values ​​(I / O value) was less than 1.5, which resulted in a problem of insufficient color density. In addition, in Patent Document 2, a polyhydric alcohol and its derivatives are contained in a fabric pretreatment agent for a sublimation transfer method in order to swell cellulose fibers. However, because such a pretreatment agent does not contain an aromatic heterocyclic compound, although it can produce a high color density, it has the problem of dye bleeding over time. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 55-163288 [Patent Document 2] Patent Publication No. 2021-42514 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above problems and circumstances, and an object of the present invention is to provide a fabric pretreatment agent, a textile printing method, and a printed fabric that can achieve both good color development and texture and suppress dye bleed-out. [Means for solving the problem]

[0006] In the course of investigating the causes of the above problems in order to solve the above problems, the present inventors discovered that it is possible to provide a fabric pretreatment agent, a textile printing method, and a printed fabric that can achieve both good color development and texture and suppress dye bleed-out by containing a solvent (having an I / O value of 1.5 or more) that swells the fibers of a fabric and an aromatic heterocyclic compound that traps the dye inside the fibers, and thus arrived at the present invention. That is, the above-mentioned problems of the present invention are solved by the following means.

[0007] 1. A fabric pretreatment agent used in sublimation transfer printing, The ratio of inorganic to organic values ​​(I / O value) is 1.5 Within the range of ~5.0 Contains solvents and aromatic heterocyclic compounds death, the aromatic heterocyclic compound is a compound having a low molecular weight in the range of 200 to 1000 and having a pyrazole ring or an imidazole ring, The solvent is contained in the fabric pretreatment agent in an amount of 5 to 95% by mass based on the entire amount of the fabric pretreatment agent, and The aromatic heterocyclic compound is contained in the fabric pretreatment agent in an amount of 1 to 30% by mass based on the entire fabric pretreatment agent. A fabric pretreatment agent characterized by the above.

[0011] 2 Item 1, characterized in that the boiling point of the solvent is within the range of 150 to 250°C. to The fabric pretreatment agent described above.

[0012] 3Item 1, characterized in that the solvent contains one or more of dimethyl sulfoxide, ethylene glycol, and propylene glycol. or paragraph 2 The fabric pretreatment agent according to claim 1.

[0016] 4 A dye-sublimation transfer printing method, Sections 1 to 5 3 1. A textile printing method comprising applying the fabric pretreatment agent according to any one of claims 1 to 10 to a fabric, and then sublimating and transferring the dye.

[0017] 5 The fabric is characterized in that it contains cellulose fibers. 4 Item 1. A textile printing method according to item 1.

[0018] 6 The temperature during transfer is higher than the boiling point of the solvent. 4 Section or Article 5 Item 1. A textile printing method according to item 1.

[0019] 7 A printed fabric comprising an aromatic heterocyclic compound and a dye, The aromatic heterocyclic compound is any one of items 1 to 5. 3 1. A printed fabric, characterized in that the aromatic heterocyclic compound is derived from the fabric pretreatment agent according to any one of claims 1 to 9. [Effects of the Invention]

[0020] The above-described means of the present invention can provide a fabric pretreatment agent, a printing method, and a printed fabric that can achieve both good color development and texture and also suppress dye bleeding-out. The mechanism by which the effects of the present invention are manifested or the mechanism of action is not clear, but is speculated as follows. The fabric pretreatment agent of the present invention contains a solvent having an inorganic / organic ratio (I / O value) of 1.5 or more, and an aromatic heterocyclic compound. The solvent with an I / O value of 1.5 or more swells the interior of the fabric fibers and acts as a dye carrier, facilitating the penetration of the dye into the fibers. The aromatic heterocyclic compound also traps the dye inside the fibers. As a result, it is believed that color development can be improved without impairing the texture. Furthermore, bleeding out of the dye over time can be prevented. Furthermore, when the solvent is removed by heat during transfer, the dye is more firmly fixed, and the bleeding-out suppression effect can be enhanced. DETAILED DESCRIPTION OF THE INVENTION

[0021] The fabric pretreatment agent of the present invention is a fabric pretreatment agent used in sublimation transfer textile printing, and is characterized by containing a solvent having an inorganic to organic ratio (I / O value) of 1.5 or more, and an aromatic heterocyclic compound. This feature is a technical feature common to or corresponding to each of the following embodiments.

[0022] In one embodiment of the present invention, the solvent is preferably contained in the range of 5 to 95% by mass based on the entire fabric pretreatment agent, in view of achieving high color density.

[0023] Furthermore, it is preferable that the aromatic heterocyclic compound is contained in the fabric pretreatment agent in an amount of 1 to 30% by mass based on the entire fabric pretreatment agent, in order to prevent bleeding out of the dye.

[0024] The I / O value of the solvent is preferably within the range of 1.5 to 5.0, since this allows the fibers of the fabric to swell. Furthermore, it is preferable that the boiling point of the solvent is within the range of 150 to 250° C., since the solvent can be removed by heat during transfer. Furthermore, it is preferable that the solvent contains at least one of dimethyl sulfoxide, ethylene glycol, and propylene glycol, since this can swell the fibers of the fabric and allow for high-density color development.

[0025] The aromatic heterocyclic compound is preferably a nitrogen-containing heterocyclic compound, which can easily trap the dye inside the fibers of the fabric and prevent the dye from bleeding out. In particular, the nitrogen-containing heterocyclic compound is preferably at least one selected from compounds having a pyrazole ring, a triazole ring, and an imidazole ring. It is preferable that the aromatic heterocyclic compound has a low molecular weight, since the aromatic heterocyclic compound can enter the interior of the fiber and capture the dye inside the fiber.

[0026] The textile printing method of the present invention is a sublimation transfer textile printing method using a dye, characterized in that the fabric pretreatment agent is applied to fabric and the dye is then sublimated. This makes it possible to achieve both good color development and texture and to suppress dye bleeding.

[0027] It is preferable that the fabric contains cellulose fibers, since this makes it possible to significantly exhibit the effects of the present invention. The temperature during transfer is preferably higher than the boiling point of the solvent, since the solvent is removed by the transfer and the dye is more firmly fixed, thereby enhancing the effect of suppressing bleeding out.

[0028] The printed fabric of the present invention is a printed fabric containing an aromatic heterocyclic compound and a dye, wherein the aromatic heterocyclic compound is an aromatic heterocyclic compound derived from the fabric pretreatment agent, thereby making it possible to provide a printed fabric that is excellent in color development and texture and in which dye bleed-out is suppressed.

[0029] The present invention, its components, and embodiments and modes for carrying out the present invention will be described below. In this application, the symbol "to" is used to mean that the numerical values ​​before and after it are included as lower and upper limits.

[0030] [Fabric pretreatment agent] The fabric pretreatment agent of the present invention (hereinafter also simply referred to as "pretreatment agent") is a fabric pretreatment agent used in sublimation transfer textile printing, and is characterized by containing a solvent having an inorganic to organic ratio (I / O value) of 1.5 or more, and an aromatic heterocyclic compound.

[0031] The ratio of inorganic value to organic value (I / O value) of the solvent contained in the pretreatment agent of the present invention is 1.5 or more, and preferably within the range of 1.5 to 5.0. The "I / O value" is the ratio of inorganic value (I) to organic value (O) (inorganic value / organic value), and is also called the "IOB value" (Inorganic Organic Balance: IOB). It is an index that indicates the polarity of a compound or component.

[0032] The I / O value is explained in detail in literature such as Organic Conceptual Diagram (by Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, items 1-16 (1954); and Area of ​​Chemistry, Vol. 11, No. 10, items 719-725 (1957). The I / O value is a value that treats the polarity of a compound or component from an organic conceptual perspective. This method is one of the functional group contribution methods in which parameters are set for each functional group, and inorganic and organic values ​​are shown for each functional group. The I / O value is calculated by dividing the properties of a compound or component into organic groups that exhibit covalent bonding and inorganic groups that exhibit ionic bonding, and positioning each at a point on a rectangular coordinate system called the organic axis and inorganic axis.

[0033] Here, the "inorganic value (I)" is a numerical value that represents the magnitude of the influence of various substituents or bonds that an organic compound has on the boiling point, based on the hydroxy group. ​Specifically, the distance between the boiling point curve of a straight-chain alcohol and that of a straight-chain paraffin is approximately 100°C when taken around the carbon number of 5, so the influence of one hydroxyl group is set to a numerical value of 100, and the value that quantifies the influence of various substituents or various bonds on the boiling point based on this value becomes the inorganic value (I) of the substituent possessed by the organic compound. For example, the inorganic value (I) of a -COOH group is 150, and the inorganic value (I) of a double bond is 2. Therefore, the inorganic value (I) of a certain organic compound means the sum of the inorganic values ​​(I) of various substituents or bonds that the compound has.

[0034] The "organic value (O)" is determined based on the influence of the carbon atom representing the methylene group on the boiling point, using the methylene group in the molecule as a unit. In other words, since the average increase in boiling point due to the addition of one carbon atom in linear saturated hydrocarbon compounds with around 5 to 10 carbon atoms is 20°C, based on this, the organicity value of one carbon atom is set to 20, and the organicity value (O) is a value that quantifies the influence of various substituents or bonds on the boiling point based on this. For example, the organicity value (O) of a nitro group (-NO2) is 70.

[0035] Generally, the closer the I / O value is to 0, the more non-polar (more hydrophobic, more organic) the organic material is, while the higher the value is, the more polar (more hydrophilic, more inorganic) the organic material is.

[0036] <Solvent> Examples of solvents having an I / O value of 1.5 or greater include ethylene glycol monoethylene ether (I / O value: 1.5), dimethyl sulfoxide (I / O value: 1.75), butyric acid (I / O value: 1.875), polyethylene glycol (I / O value: 2.0), isobutyric acid (I / O value: 2.143), 2,3-butanediol (I / O value: 2.5), trimethylolethane (I / O value: 3.0), propylene glycol (I / O value: 3.3), polypropylene glycol (I / O value: 3.3), and ethylene glycol (I / O value: 5.0). Among these, the solvent preferably contains at least one of dimethyl sulfoxide, ethylene glycol, and propylene glycol, as this allows the fibers of the fabric to swell and allows for high-intensity color development.

[0037] The solvent according to the present invention preferably has a boiling point within the range of 150 to 250° C. Examples of solvents having a boiling point within the range of 150 to 250° C. include propylene glycol (188° C.), ethylene glycol (197° C.), dimethyl sulfoxide (189° C.), and 2,3-butanediol (177° C.).

[0038] The solvent according to the present invention is preferably contained in the fabric pretreatment agent in an amount of 5 to 95% by mass, more preferably 15 to 50% by mass, based on the total mass of the fabric pretreatment agent, from the viewpoint of color density.

[0039] <Aromatic heterocyclic compounds> The pretreatment agent of the present invention contains an aromatic heterocyclic compound. In the present invention, an aromatic heterocyclic compound refers to a compound having aromaticity and consisting of carbon and heteroatoms other than carbon as elements constituting an aromatic ring, but does not include a case where the only element constituting the aromatic ring is carbon and the heteroatom constitutes a substituent substituted on the aromatic ring. The aromatic heterocyclic compound according to the present invention is preferably a nitrogen-containing heterocyclic compound in which the heteroatom constituting the aromatic ring is selected from oxygen, nitrogen, and sulfur atoms, more preferably a nitrogen atom, from the viewpoint of high dye capture ability.

[0040] Examples of the nitrogen-containing heterocyclic compound include compounds having a pyrazole ring, a triazole ring, an imidazole ring, a triazine ring, a pyridine ring, a pyrazole ring, an aridine ring, an indole ring, a quinoline ring, a pyrrole ring, and a thiophene ring. In particular, at least one selected from compounds having a pyrazole ring, a triazole ring, and an imidazole ring is preferred in terms of complementing the dye. Specifically, exemplary compounds (1) to (11) represented by the following structural formulas may be mentioned.

[0041] [ka]

[0042] [ka]

[0043] The aromatic heterocyclic compound preferably has a low molecular weight so that the dye can be trapped inside the fibers of the fabric. The low molecular weight is, for example, within the range of 200 to 1,000.

[0044] From the viewpoint of dye capture, the aromatic heterocyclic compound is preferably contained in the fabric pretreatment agent in an amount of 1 to 30% by mass, and more preferably in an amount of 10 to 20% by mass.

[0045] <Water> The pretreatment agent of the present invention may contain water. The water is not particularly limited, and may be ion-exchanged water, distilled water, or pure water. The water content in the pretreatment agent is preferably within a range from 0 to 95% by mass, and more preferably within a range from 0 to 50% by mass.

[0046] <Other ingredients> The pretreatment agent according to the present invention may further contain other components in addition to those described above, as necessary. Examples of such other components include surfactants, preservatives, pH adjusters, etc.

[0047] There are no particular limitations on the surfactants that can be used, but when the ink contains an anionic compound as a constituent, the ionicity of the surfactant is preferably anionic, nonionic, or betaine type. Specifically, preferred are fluorine-based or silicone-based surfactants that have a high ability to reduce static surface tension, anionic surfactants such as dioctyl sulfosuccinate and sodium dodecyl sulfate that have a high ability to reduce dynamic surface tension, and nonionic surfactants such as relatively low-molecular-weight polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, acetylene glycols, Pluronic surfactants (Pluronic is a registered trademark), and sorbitan derivatives. It is also preferred to use a fluorine-based or silicone-based surfactant in combination with a surfactant that has a high ability to reduce dynamic surface tension.

[0048] Examples of preservatives include aromatic halogen compounds (eg, Preventol CMK), methylene dithiocyanate, halogen-containing nitrogen-sulfur compounds, 1,2-benzisothiazolin-3-one (eg, PROXELGXL), and the like.

[0049] Examples of pH adjusters include citric acid, sodium citrate, hydrochloric acid, sodium hydroxide, and the like.

[0050] <Properties of pretreatment agent> The viscosity of the pretreatment agent at 25°C can be adjusted as appropriate depending on the method of application to the fabric. For example, when the pretreatment agent is applied by inkjet printing, the viscosity of the pretreatment agent is preferably within the range of 4 to 20 mPa s. The viscosity of the pretreatment agent can be measured at 25°C using an E-type viscometer.

[0051] <Fabric> The material of the fibers constituting the fabric to which the pretreatment agent of the present invention is applied is not particularly limited, and examples thereof include natural fibers (hydrophilic fibers) such as cellulose fibers (natural cotton), hemp, wool, and silk, and chemical fibers such as rayon, vinylon, nylon, acrylic, polyurethane, polyester, and acetate.

[0052] The fabric preferably contains natural fibers such as cellulose fibers, hemp, wool, and silk, and it is particularly preferable that the fabric contains cellulose fibers because the effects of the present invention can be significantly exhibited. The fabric may be made of one type of natural fiber or two or more types. When the fabric contains natural fibers, it may further contain one or more types of chemical fibers.

[0053] The fabric may be any form of fabric, such as woven fabric, nonwoven fabric, or knitted fabric, made from these fibers. The fabric may also be a blended woven fabric or blended nonwoven fabric made from two or more types of fibers. As described above, the fabric preferably contains cellulose fibers. When the fabric contains cellulose fibers and fibers other than cellulose fibers, the other fibers preferably contain polyester fibers.

[0054] The ratio of natural fibers and chemical fibers in the fibers constituting the fabric is expressed as the mass % of natural fibers and the mass % of chemical fibers contained relative to the total amount of the fabric (total amount of natural fibers and chemical fibers). When the fabric of the present invention contains natural fibers and optionally chemical fibers, the ratio of natural fibers in the fabric is preferably in the range of 5 to 100 mass % and the ratio of chemical fibers is preferably in the range of 0 to 95 mass %. For example, when the fabric contains cellulose fibers and polyester fibers, the ratio of cellulose fibers is preferably in the range of 35 to 100 mass % and the ratio of polyester fibers is preferably in the range of 0 to 65 mass %.

[0055] [Printing method] The textile printing method of the present invention is a sublimation transfer textile printing method using a dye, and is characterized by comprising a step (i) pretreatment step) of applying the pretreatment agent of the present invention to a fabric, and a step (ii) sublimation transfer step) of sublimating the dye before the applied pretreatment agent dries.

[0056] The textile printing method of the present invention is carried out using an ink containing a dye.

[0057] [ink] The ink according to the present invention preferably contains a dye, a solvent, and water.

[0058] <dye> The dye is preferably a disperse dye. Disperse dyes are dyes that are insoluble or slightly soluble in water. As disperse dyes, sublimation dyes that are insoluble or slightly soluble in water and have the property of sublimating upon heating are preferred. Here, "insoluble or slightly soluble in water" means that the solubility in water at 25°C is 10 mg / L or less, preferably 5 mg / L or less, and more preferably 1 mg / L or less.

[0059] The type of disperse dye is not particularly limited, and includes azo dyes, anthraquinone dyes, etc. Specifically, examples of sublimation dyes among disperse dyes include the following dyes.

[0060] CIDisperse Yellow3, 4, 5, 7, 9, 13, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 6 4, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 114, 116, 118, 119, 122, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 17 9, 180, 182, 183, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224, etc.

[0061] CIDisperse Orange1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 47, 48, 49, 50, 53 , 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139, 142, etc.

[0062] C.I. Disperse Red 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 289, 298, 302, 303, 310, 311, 312, 320, 324, 328, etc.

[0063] C.I. Disperse Violet 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, 77, etc.

[0064] C.I. Disperse Green 9, etc. C.I. Disperse Brown 1, 2, 4, 9, 13, 19, etc.

[0065] CIDisperse Blue3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 79, 81, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143, 146, 148, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 267, 268, 270, 284, 285, 287, 288, 291, 293, 295, 297, 301, 315, 330, 333, 359, 360, etc. CIDisperseBlack1, 3, 10, 24 etc.

[0066] The molecular weight of the disperse dye is not particularly limited, but for example, when an ink applied to a transfer medium is transferred to a resin-coated fabric as described below to form an image (sublimation printing), the molecular weight is preferably small (e.g., 200 to 350) from the viewpoint of facilitating sublimation of the disperse dye. On the other hand, the molecular weight is preferably moderately large (e.g., 350 to 500) from the viewpoint of preventing the disperse dye from escaping from the fabric. The disperse dyes contained in the ink may or may not be crystallized. As a method for applying ink to an object, for example, a coating method, an inkjet method can be mentioned, and the use of the inkjet method makes it possible to perform printing with high precision.

[0067] The average particle size of the dispersible dye in the ink is not particularly limited, but from the viewpoint of ejection stability by the inkjet method, it may be, for example, 300 nm or less. The average particle size can be determined by a commercially available particle size measuring device using a light scattering method, an electrophoresis method, a laser Doppler method, or the like, and examples of particle size measuring devices include the Zetasizer 1000 manufactured by Malvern Instruments.

[0068] The content of disperse dye in the ink is not particularly limited, but is preferably in the range of 2 to 10% by mass of the ink. If the content of disperse dye is 2% by mass or more, it is easy to form a high-density image, and if it is 10% by mass or less, the viscosity of the ink does not become too high, so ejection stability is less likely to be impaired. From the same perspective, the content of disperse dye is more preferably in the range of 5 to 10% by mass of the ink.

[0069] <Water> The water may be ion-exchanged water, distilled water, or pure water. The water content in the ink is preferably in the range of 90 to 98% by mass, and more preferably in the range of 90 to 95% by mass.

[0070] <Solvent> The ink may contain other solvents in addition to water. The other solvents are not particularly limited, but are preferably water-soluble organic solvents. The total content of water and the water-soluble organic solvent is preferably 90 to 98% by mass, more preferably 90 to 95% by mass, of the ink.

[0071] Examples of the water-soluble organic solvent include alcohols (e.g., methanol, ethanol, propanol, pentanol, hexanol, cyclohexanol, and benzyl alcohol), polyhydric alcohols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, glycerin, and compounds represented by the following general formula (1)), polyhydric alcohol ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether), and Examples of suitable organic solvents include methyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; amines (e.g., ethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, and triethylenetetramine); amides (e.g., formamide, N,N-dimethylformamide, and N,N-dimethylacetamide); heterocycles (e.g., 2-pyrrolidone, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 2-oxazolidone, and 1,3-dimethyl-2-imidazolidine); sulfoxides (e.g., dimethyl sulfoxide); and sulfones (e.g., sulfolane).

[0072] [ka]

[0073] [In general formula (1), R 11 represents an ethylene glycol group or a propylene glycol group, x, y, and z are all positive integers, and x+y+z=3 to 30.]

[0074] Among water-soluble organic solvents, when the fabric contains hydrophilic fibers such as cellulose fibers, it is preferable that the ink does not easily thicken upon drying, from the viewpoint of promoting penetration of the ink into the fabric and preventing loss of ejection stability in inkjet printing. Therefore, it is preferable that the ink contains a high-boiling-point solvent with a boiling point of 200°C or higher.

[0075] The high-boiling solvent having a boiling point of 200°C or higher may be any water-soluble organic solvent having a boiling point of 200°C or higher, and is preferably a polyol or a polyalkylene oxide. Examples of polyols having a boiling point of 200°C or higher include dihydric alcohols such as 1,3-butanediol (boiling point 208°C), 1,6-hexanediol (boiling point 223°C), and polypropylene glycol; and trihydric or higher alcohols such as glycerin (boiling point 290°C) and trimethylolpropane (boiling point 295°C). Examples of polyalkylene oxides having a boiling point of 200°C or higher include ethers of dihydric alcohols such as diethylene glycol monoethyl ether (boiling point 202°C), triethylene glycol monomethyl ether (boiling point 245°C), tetraethylene glycol monomethyl ether (boiling point 305°C), tripropylene glycol monoethyl ether (boiling point 256°C), and polypropylene glycol, as well as ethers of trihydric or higher alcohols such as glycerin (boiling point 290°C) and hexanetriol.

[0076] The content of the water-soluble organic solvent is preferably within the range of 20 to 70% by mass of the ink. When the content of the water-soluble organic solvent is 20% by mass or more, the dispersibility and ejection properties of the disperse dye are more likely to be improved, and when it is 70% by mass or less, the drying properties of the ink are less likely to be impaired.

[0077] <Other ingredients> The ink may further contain other components as necessary, such as dispersants, surfactants, preservatives, and pH adjusters.

[0078] (dispersant) The dispersant can be selected depending on the type of disperse dye. Examples of dispersants include formalin condensates of sodium creosote oil sulfonate, formalin condensates of sodium cresol sulfonate and sodium 2-naphthol-6-sulfonate, formalin condensates of sodium cresol sulfonate, formalin condensates of sodium phenolsulfonate, formalin condensates of sodium β-naphtholsulfonate, formalin condensates containing sodium β-naphthalenesulfonate and sodium β-naphtholsulfonate, alkylene oxides including ethylene oxide and propylene oxide, fatty alcohols, fatty amines, fatty acids, phenols, alkylatable compounds including alkylphenols and carboxylic acid amines, lignin sulfonates, sodium paraffin sulfonates, and α-olefins. and maleic anhydride copolymers, as well as the well-known comb block polymers.

[0079] Examples of comb block polymers include DISPERBYK-190, DISPERBYK-194N, DISPERBYK-2010, DISPERBYK-2015, and BYK-154 manufactured by BYK-Chemie ("DISPERBYK" and "BYK" are registered trademarks of the company).

[0080] The content of the dispersant is not particularly limited, but is preferably in the range of 20 to 200 parts by mass relative to 100 parts by mass of the disperse dye. When the content of the dispersant is 20 parts by mass or more, the dispersibility of the disperse dye is likely to be further improved, and when it is 200 parts by mass or less, it is easy to suppress the decrease in ejection property due to the dispersant.

[0081] (surfactants, preservatives, pH adjusters) The surfactants, preservatives, and pH adjusters that can be used are the same as those that can be used in the pretreatment agent.

[0082] <Ink properties> The viscosity of the ink at 25°C is not particularly limited as long as it provides good ejection properties using an inkjet system, but is preferably in the range of 3 to 20 mPa·s, and more preferably in the range of 4 to 12 mPa·s. The viscosity of the ink can be measured at 25°C using an E-type viscometer.

[0083] (i) Pretreatment process In the pretreatment step, the pretreatment agent is applied to at least a part of the surface of the fabric. The pretreatment agent may be applied to the entire surface of the fabric, or may be applied selectively to only the areas to be dyed with disperse dyes according to the image to be printed.

[0084] The method for applying the pretreatment agent to the fabric can be any known method without any particular limitation. Specific examples include a spray method, a mangle method (a pad method or a dipping method), a coating method, an inkjet method, etc. For example, in the sublimation transfer step described below, the inkjet method is preferred from the viewpoint of being able to apply the ink containing a disperse dye continuously, and the mangle method or coater method is preferred from the viewpoint of applying a predetermined amount of the pretreatment agent in a short time.

[0085] In the mangle method, a fabric is immersed in a pretreatment agent stored in a bath and then squeezed to adjust the amount of pretreatment agent applied. The temperature of the pretreatment agent is not particularly limited, but can be set to 15 to 30°C. The conditions for applying the ink in the inkjet method can be the same as those for applying the ink in the dyeing process.

[0086] The amount of the pretreatment agent to be applied is not particularly limited, and can be adjusted depending on the content of the solvent and aromatic heterocyclic compound in the pretreatment agent, the amount of ink to be applied, and other factors.

[0087] <Drying of pre-treatment agent> After applying the pretreatment agent to the fabric, a step of removing the liquid medium from the coating film of the pretreatment agent applied to the fabric, i.e., a drying step, may be carried out, but it is preferable that the solvent remains. The drying method is not particularly limited, and heating with hot air, a hot plate, or a heat roller is preferred. From the viewpoint of sufficiently removing the liquid medium in a short time, heat drying is more preferred. The drying temperature is preferably within the range of 100 to 130°C.

[0088] (ii) Sublimation transfer process The sublimation transfer process is a process in which a transfer image is formed on a transfer medium, and the transfer image formed on the transfer medium is thermally transferred onto the fabric to which the pretreatment agent has been applied in the pretreatment process. Here, it is preferable to thermally transfer the transfer image onto the fabric before the pretreatment agent applied to the fabric has completely dried. This allows the solvent in the pretreatment agent to easily swell the fabric fibers, acting as a carrier for the transferred dye, which facilitates penetration of the dye into the fibers and improves color development and texture. Furthermore, the aromatic heterocyclic compound in the pretreatment agent captures the transferred dye, preventing it from bleeding out. Specifically, the transfer image formed on the transfer medium is formed using the ink described above containing a dispersible dye and a liquid medium (solvent and water).

[0089] Specifically, first, ink is applied to a transfer medium by a known ink application method, for example, an inkjet method, and then dried to form an ink layer (transfer image) corresponding to the printed image.

[0090] The transfer medium used in the present invention is not particularly limited as long as it is capable of forming an ink layer on the surface of the transfer medium and further capable of transferring the ink layer to fabric, for example, it is capable of not interfering with the sublimation of the sublimation dye during transfer. For example, the transfer medium is preferably paper having an ink-receiving layer formed on its surface using inorganic fine particles such as silica, and examples of the transfer medium include dedicated paper for inkjet printing and transfer paper.

[0091] Next, the surface of the image to be transferred on the transfer medium is brought into contact with the surface of the fabric (pre-treated surface) to which the pre-treatment agent has been applied, and heated (heat pressed) to transfer the image. As a result, the sublimation dye as a dispersible dye in the image to be transferred formed on the transfer medium is sublimated and transferred to the fabric, specifically to the pre-treatment agent applied to the fabric, thereby printing the desired image on the fabric.

[0092] The transfer temperature (heat press temperature) varies depending on the sublimation temperature of the sublimation dye used as the dispersible dye, but is preferably within a range of, for example, 180 to 210°C. In particular, it is preferable that the temperature be higher than the boiling point of the solvent contained in the pretreatment agent, since this allows the solvent to be removed by transfer, further immobilizing the dye and enhancing the bleed-out suppression effect.

[0093] The pressing pressure is 200 to 500 g / cm for flat molds. 2 In the case of continuous type, the range is 2 to 6 kg / cm 2 It is preferable that the range is within the range of The pressing time is preferably 30 to 180 seconds, although it depends on the temperature.

[0094] [Printed fabric] The printed fabric of the present invention is a printed fabric containing an aromatic heterocyclic compound and a dye, wherein the aromatic heterocyclic compound is an aromatic heterocyclic compound derived from the fabric pretreatment agent of the present invention. That is, the printed fabric of the present invention is obtained by thermally transferring a transfer image formed on a transfer medium using a disperse dye onto a fabric to which the fabric pretreatment agent containing a solvent having an I / O value of 1.5 or more and an aromatic heterocyclic compound has been applied. In the present invention, the term "printed fabric containing an aromatic heterocyclic compound and a dye" means a fabric in which the aromatic heterocyclic compound and the dye are present due to a physical interaction so as to fill the gaps between the fibers constituting the fabric, for example, in a physically adsorbed state, or in which the fibers, the aromatic heterocyclic compound, and the dye are chemically bonded to each other, i.e., in a chemically adsorbed state. [Example]

[0095] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, operations were carried out at room temperature (25°C). Furthermore, unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass," respectively.

[0096] [Preparation of pretreatment agent] Pretreatment agents 1 to 17 were prepared by mixing a solvent, an aromatic heterocyclic compound, a surfactant, and ion-exchanged water to obtain the compositions shown in Table I below. The compounds used as the aromatic heterocyclic compounds are the above-mentioned exemplary compounds (1), (2) and (10).

[0097] [Table 1]

[0098] [Ink preparation] <Preparation of Ink 1> (Preparation of Dispersion) Disperbyk-190 (BYK Japan, acid value 10 mgKOH / g) as a dispersant was mixed with ion-exchanged water until homogeneous, and then Disperse Red 60 as a disperse dye was added and premixed. The mixture was dispersed until the Z-average particle size measured by dynamic light scattering was within the range of 150-200 nm, preparing a dispersion with a disperse dye concentration of 20% by mass. The amounts of dispersant, ion-exchanged water, and disperse dye were adjusted so that the disperse dye content was 20% by mass of the total dispersant mass and the solids content of the dispersant was 30% by mass of the total disperse dye mass. The Z-average particle size was measured by dynamic light scattering using a sand grinder filled with 0.5 mm zirconia beads at a volume ratio of 50%, using a Zetasizer 1000 manufactured by Malvern ("Zetasizer" is a registered trademark of the company).

[0099] (Ink Preparation) The obtained dispersion was mixed with 30% by mass of glycerin as a solvent, 25% by mass of ethylene glycol as a solvent, Proxel GXL as a preservative, and sodium citrate hydrate as a pH adjuster in appropriate amounts, and then mixed with ion-exchanged water to make a total of 100% by mass. The mixture was then filtered through a 1 μm mesh filter to obtain Ink 1 (magenta sublimation ink).

[0100] [Image formation] (1) Pretreatment method The fabric used was cotton broadcloth 40 (100% cotton). The fabric was immersed in a bath filled with the pretreatment agent prepared above, and excess pretreatment agent was squeezed out with a mangle roll at a pickup rate (amount of treatment solution applied to the weight of the fabric) of 80%. The temperature in the bath was set to 20 to 25°C.

[0101] (2) Applying ink to transfer paper Next, an inkjet printer equipped with an inkjet head (Konica Minolta Head KM1024iMAE) was prepared as an image forming apparatus. Ink 1 prepared above was then ejected from the nozzles of the inkjet head to form a solid image on an A4 size adhesive sublimation transfer paper (manufactured by System Graphie) as transfer paper. Specifically, an image (200 mm x 200 mm in total) containing a fine line grid, gradation, and solid areas was formed at 540 dpi in the main scan direction and 720 dpi in the sub-scan direction. dpi represents the number of ink droplets (dots) per 2.54 cm. The ejection frequency was 22.4 kHz. The ink-applied transfer paper was then dried in a dryer at 50 to 80°C for 30 seconds.

[0102] (3) Transferring ink to fabric Next, the transfer paper to which the ink (ink layer) was applied was transferred using a transfer device (heat press machine) at 200°C for 50 seconds with a pressing pressure of 300 g / cm. 2 Thereby, the ink on the transfer paper was transferred onto the pretreated fabric, and an image was obtained.

[0103] [evaluation] The resulting image-formed product was evaluated as follows. <Color development> The image density was measured using a spectrophotometer (Konica Minolta) and the K / S value was calculated. The K / S value is an index of surface color density defined by the following formula. The calculated K / S value was used to evaluate color development according to the following criteria. Kubelka-Munk equation: K / S=(1-R) 2 / 2S (K: light absorption coefficient, S: light scattering coefficient, R: surface reflectance) A larger K / S value means a higher color density, and a smaller K / S value means a lower color density. In the following criteria, ranks 2 to 5 are considered to be acceptable for practical use. (standard) 5: K / S value is 15 or more 4: K / S value is 12 or more but less than 15 3: K / S value is 10 or more but less than 12 2: K / S value is 8 or more but less than 10 1: K / S value less than 8

[0104] <Bleed out> The colored image-formed product was left in a high-humidity environment (ambient temperature 20°C, humidity 90% RH or more) for one day, and the K / S value was calculated in the same manner as in the color development evaluation. The color density after color development (K / S value during color development evaluation) was compared with the color density after being left in the high-humidity environment to calculate the density loss rate, which was evaluated according to the following criteria. The density loss rate was calculated by (K / S value during color development - K / S value after being left in the high-humidity environment) / (K / S value during color development). In the following criteria, ranks 2 to 5 were considered to be acceptable for practical use. (standard) 5: Concentration reduction rate is less than 20% 4: Concentration reduction rate is 20% or more but less than 25% 3: Concentration reduction rate is 25% or more but less than 30% 2: Concentration reduction rate is 30% or more but less than 50% 1: Concentration reduction rate is 50% or more

[0105] <Texture> The texture of the image-formed product and the fabric was evaluated sensorily by touching with the fingers, and was evaluated based on the following criteria. (standard) 5: The original softness of the fabric is maintained, almost unchanged (from before image formation) 4: The paper is slightly stiffer than before the image was formed, but the texture of the fabric is not impaired and there is no problem in practical use. 3: The paper is slightly stiffer than before the image formation, and the texture of the fabric has changed slightly, but this is not a problem for practical use. 2: The paper is slightly stiffer than before the image formation, and the texture of the fabric has changed slightly, but this is not a problem for practical use. 1: The fabric has become harder than before image formation, the texture of the fabric has been significantly impaired, and it is at a level that is problematic for practical use.

[0106] [Table 2]

[0107] As shown by the above results, it is recognized that the image formed using the pretreatment agent of the present invention is superior in color development and texture to the comparative example, and that bleeding out can also be suppressed.

Claims

1. A fabric pretreatment agent used in sublimation transfer printing, comprising: The composition contains a solvent having an inorganic / organic ratio (I / O value) in the range of 1.5 to 5.0, and an aromatic heterocyclic compound; the aromatic heterocyclic compound is a compound having a low molecular weight in the range of 200 to 1000 and having a pyrazole ring or an imidazole ring, The solvent is contained in a range of 5 to 95% by mass based on the entire fabric pretreatment agent, and The fabric pretreatment agent is characterized in that the aromatic heterocyclic compound is contained in an amount within the range of 1 to 30% by mass based on the entire fabric pretreatment agent.

2. 2. The fabric pretreatment agent according to claim 1, wherein the boiling point of the solvent is within the range of 150 to 250°C.

3. 3. The fabric pretreatment agent according to claim 1, wherein the solvent contains at least one of dimethyl sulfoxide, ethylene glycol, and propylene glycol.

4. A dye sublimation transfer printing method, A textile printing method comprising applying the fabric pretreatment agent according to any one of claims 1 to 3 to a fabric, and then sublimating and transferring the dye.

5. 5. The textile printing method according to claim 4, wherein the fabric contains cellulose fibers.

6. 6. The textile printing method according to claim 4, wherein the temperature during transfer is higher than the boiling point of the solvent.

7. A printed fabric comprising an aromatic heterocyclic compound and a dye, A printed fabric, wherein the aromatic heterocyclic compound is an aromatic heterocyclic compound derived from the fabric pretreatment agent according to any one of claims 1 to 3.

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