Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
  • C09B1/16—Amino-anthraquinones
  • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
  • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
  • C09B1/28—Dyes with amino groups substituted by hydrocarbon radicals substituted by alkyl, aralkyl or cyclo alkyl groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B25/00—Quinophthalones
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B29/00—Monoazo dyes prepared by diazotising and coupling
  • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
  • C09B29/08—Amino benzenes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/30—Ink jet printing
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06Q—DECORATING TEXTILES
  • D06Q1/00—Decorating textiles
  • D06Q1/12—Decorating textiles by transferring a chemical agent or a metallic or non-metallic material in particulate or other form, from a solid temporary carrier to the textile
  • D06Q1/14—Decorating textiles by transferring a chemical agent or a metallic or non-metallic material in particulate or other form, from a solid temporary carrier to the textile by transferring fibres, or adhesives for fibres, to the textile

Definitions

• the present invention relates to a dye dispersion and a method for printing hydrophobic fibers using the dye dispersion.
• the hydrophobic fiber cloth such as polyester fiber is generally dyed with a coloring material insoluble in water. Therefore, as a water-based ink for printing hydrophobic fibers by an inkjet recording method, it is generally necessary to use a dispersed ink in which a water-insoluble coloring material is dispersed in water and has good performance such as dispersion stability.
• the inkjet printing method for hydrophobic fibers typified by polyester fibers can be roughly classified into the following two methods.
• the direct printing method in which the dye in the ink is dyed on the fibers by heat treatment such as high temperature steaming, and ink is applied (printed) to an intermediate recording medium (dedicated transfer paper, etc.).
• This is a sublimation transfer method in which the ink-imparted surface of the intermediate recording medium and the hydrophobic fibers are overlapped with each other, and then the dye is transferred from the intermediate recording medium to the fiber side by heat.
• the sublimation transfer method is mainly used for printing of banners and the like, and an easy sublimation type dye having excellent transfer suitability to polyester by heat treatment is used in the ink.
• a processing process (1) Printing process: A process of applying dye ink to an intermediate recording medium by an inkjet printer.
• the inkjet ink used in the sublimation transfer method is mainly a water-based ink, and a sublimative dye selected from a water-insoluble disperse dye group and an oil-soluble dye group is dispersed and stabilized in water using a dispersant.
• a water-soluble organic solvent as a moisturizing agent (anti-drying agent), a surfactant as a surface tension adjusting agent, and other additives (pH adjusting agent, antiseptic / anti-inking agent, defoaming agent, etc.) Is used to optimize physical properties (physical properties) such as particle size, viscosity, surface tension, and pH to make ink (see Patent Document 1).
• inkjet printing it is important to be able to stably eject ink from the plate in which the nozzles of the print head are arranged, but in water-based ink, ejection trouble caused by evaporation of water in the ink near the nozzle plate occurs. It is easy to happen.
• ejection trouble for example, when the ink composition adheres and dries on the plate, it cannot be quickly removed by the cleaning operation of the printer, causing poor ink ejection (flying bending, etc.) during printing. That can be mentioned.
• black is usually expressed by combining a plurality of dyes.
• the sublimation transfer ink is applied (printed) to an intermediate recording medium (dedicated transfer paper, etc.) by an inkjet printer, and the ink application (print) surface of the intermediate recording medium is used.
• the sublimable dye is transferred to the object to be dyed by a heat-bonding method using a heat-bonding roller, a heat-pressing machine, or the like on a superposed object (polyester fiber or the like) to be dyed.
• the speed of inkjet printing is higher, and there is a demand for ink design for inkjet ink that can handle the higher speed.
• an ink receiving layer is formed on the surface of inorganic fine particles such as silica, and a special paper for inkjet having a relatively large basis weight so that a large amount of ink can be applied.
• transfer paper having a smaller basis weight and transfer paper having a smaller ink receiving layer have been used, and high transfer efficiency and high dyeing density are strongly required with a small amount of ink.
• black ink in which the hue of black is not blurred depending on the sublimation transfer conditions and the sublimation rate is uniform.
• Patent Document 2 describes a black ink for inkjet used as a disperse dye ink for printing, which is maximized in a specific wavelength range in ultraviolet-visible spectral absorption of a water-soluble organic solvent containing glycol ether and a solution dissolved in acetone.
• a black ink for inkjet characterized by containing the first to fourth disperse dyes having an absorption wavelength is described, but the ink directly applied to the pretreated polyester fiber in the direct printing method is mentioned.
• the technical study on the dye having sublimation property that can be used in the sublimation transfer method has not been made, and the leveling property and dyeing performance in high-concentration dyeing have not been disclosed.
• the dyeing density is high and the dyeing density is high even when a transfer paper having a small basis weight or a transfer paper having a small ink receiving layer is used while maintaining stable printability and storage stability of black ink. It was difficult to obtain a high-quality dyed product having excellent color playability and light resistance.
• a dyed product having excellent color rendition can be produced, and sublimation transfer efficiency is high even when a transfer paper having a small basis weight or a transfer paper having a small ink receiving layer is used. It is an object of the present invention to provide a dye dispersion liquid for an inkjet printing ink, which can obtain a dyed product having a high concentration and can obtain a high-quality dyed product having excellent light resistance.
• the present inventors have at least one dye represented by the following formula (1), at least one yellow dye, and at least one blue dye.
• the present invention has been completed by finding that a dye dispersion containing more than one species solves the above-mentioned problems. That is, the present invention relates to the following 1) to 10).
• R 1 and R 2 independently have a hydrogen atom and a C 1-4 alkyl group which may have a substituent, an acetoxyethyl group and a cyclic alkyl which may have a substituent.
• a group or an aryl group which may have a substituent is represented
• R 3 represents a hydrogen atom, a C 1-3 alkyl group which may have a substituent or a halogen atom
• R 4 represents a hydrogen atom. , Or a halogen atom.
• R 1 and R 2 are independently C 1-4 alkyl groups, and R 3 is selected from the group consisting of a hydrogen atom and a C 1-3 alkyl group 1). Or the dye dispersion according to 2). 4) 2) or 3), wherein the dispersant contains at least one dispersant selected from the group consisting of a styrene- (meth) acrylic copolymer, a formalin condensate of an aromatic sulfonic acid or a salt thereof.
• Dye dispersion 5) The dye dispersion according to any one of 1) to 4) further containing an additive.
• a method for printing hydrophobic fibers wherein the hydrophobic fibers are brought into contact with the adhesion surface of the droplets of the dye dispersion in the intermediate recording medium and heat-treated to transfer the recorded image to the hydrophobic fibers.
• the dye dispersion contains at least one of the above formula (1).
• R 1 and R 2 may independently have a hydrogen atom and a C 1-4 alkyl group which may have a substituent, an acetoxyethyl group and a cyclic which may have a substituent. It represents an alkyl group or an aryl group which may have a substituent, R 3 represents a hydrogen atom, a C 1-3 alkyl group which may have a substituent or a halogen atom, and R 4 represents hydrogen. Represents an atom or a halogen atom.
• Examples of the C 1-4 alkyl group which may have the above-mentioned substituent include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Examples thereof include an ethyl group, and an ethyl group is preferable.
• Examples of the C 1-3 alkyl group which may have the above-mentioned substituent include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group and the like, and a methyl group is preferable.
• Examples of the cyclic alkyl group that may have the above-mentioned substituent include a cyclopentyl group and a cyclohexyl group.
• halogen atom examples include fluorine, chlorine, bromine, iodine and the like, and bromine is preferable.
• the C 1-4 alkyl group which may have the above-mentioned substituent, the cyclic alkyl group which may have a substituent, and the aryl group which may have a substituent have a substituent.
• the substituent in the C 1-3 alkyl group is not particularly limited, and examples thereof include a hydroxyl group, a sulfo group, a carboxyl group, a nitro group, a halogen atom, a cyano group, an alkoxy group, and an aryloxy group.
• the halogen atom may be the same as above.
• Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-butoxy group and the like.
• Examples of the aryloxy group include a phenoxy group and a naphthoxy group.
• R 1 and R 2 are independently C 1-4 alkyl groups, and R 3 is selected from the group consisting of a hydrogen atom and a C 1-3 alkyl group. preferable.
• R 1 and R 2 are independently ethyl groups
• R 3 is a hydrogen atom or a methyl group
• R 4 is a bromine atom
• the above dye dispersion contains at least one yellow dye.
• the yellow dye is generally not limited as long as it has a yellow hue, but is preferably a water-insoluble yellow dye, and among the water-insoluble yellow dyes, a disperse dye-based yellow dye or an oil-soluble dye.
• a dye-based yellow dye is more preferable, and C.I. I. Disperse yellow dye, C.I. I. More preferably, it is a solvent yellow dye.
• the disperse yellow dye include C.I. I. Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 64, 71, 79, 82, 86 and the like can be mentioned.
• Examples of the solvent yellow dye include C.I. I.
• Solvent Yellow 114, 163 and the like can be mentioned. These dyes can be used alone or in combination of two or more. Examples of the dye include C.I. I. Disperse Yellow 7, 54, C.I. I. It is preferable to use Solvent Yellow 114, and C.I. I. It is particularly preferable to use Disperse Yellow 54.
• the above dye dispersion contains at least one type of blue dye.
• the blue dye is not particularly limited as long as it is a dye having a blue hue, but is preferably a water-insoluble blue dye, and among the water-insoluble blue dyes, a disperse dye-based blue dye or an oil-soluble dye.
• a dye-based blue dye is more preferable, and C.I. I. Disperse blue dye, C.I. I. More preferably, it is a solvent blue dye.
• C. I. Examples of the disperse blue dye include C.I. I.
• Disperse Blue 3 5, 19, 26, 26: 1, 35, 55, 56, 58, 60, 64, 64: 1, 72, 72: 1, 81, 81: 1, 91, 95, 108, 131 , 141, 145, 334, 359, 360, 336 and the like.
• the solvent blue dye examples include C.I. I. Examples thereof include Solvent Blue 3, 36, 63, 83, 105 and 111. These dyes can be used alone or in combination of two or more. Examples of the dye include C.I. I. Disperse Blue 60, 72, 334, 359, 360 is preferred, and C.I. I. Disperse blue 359, 360 is more preferred, and C.I. I. It is more preferable to use Disperse Blue 359 and 360 in combination.
• the total content ratio of the dye represented by the above formula (1), the yellow dye, and the blue dye in the dye dispersion can be arbitrarily set, but with respect to the total mass of the dye dispersion. , All are usually 1 to 20%, preferably 2 to 15%, and more preferably 3 to 10% on a mass basis (mass%).
• the dye dispersion may further contain a dispersant.
• a styrene- (meth) acrylic copolymer for example, a formalin condensate of aromatic sulfonic acid, or a salt thereof can be used.
• the styrene- (meth) acrylic copolymer is a copolymer of a styrene-based monomer and a (meth) acrylic-based monomer.
• (meth) acrylic means "acrylic" and / or "methacryl”.
• copolymers include ( ⁇ -methyl) styrene-acrylic acid copolymer, ( ⁇ -methyl) styrene-acrylic acid-acrylic acid ester copolymer, and ( ⁇ -methyl) styrene-methacrylic acid copolymer.
• Polymers ( ⁇ -methyl) styrene-methacrylic acid-acrylic acid ester copolymers, ( ⁇ -methyl) styrene- (anhydrous) maleic acid copolymers, acrylic acid esters- (anhydrous) maleic acid copolymers, ( ⁇ -Methyl) styrene-acrylic acid ester- (anhydrous) maleic acid copolymer, acrylic acid ester-allylsulfonic acid ester copolymer, acrylic acid ester-styrenesulfonic acid copolymer, ( ⁇ -methyl) styrene-methacrylic acid Sulphonic acid copolymers, polyester-acrylic acid copolymers, polyester-acrylic acid-acrylic acid ester copolymers, polyester-methacrylic acid copolymers, polyester-methacrylic acid-acrylic acid copolymer esters; etc.
• the compound containing an aromatic hydrocarbon group is preferably styrene.
• ( ⁇ -methyl) styrene is used in this specification as a meaning including ⁇ -methylstyrene and styrene.
• the dispersant contains at least one dispersant selected from the group consisting of a styrene- (meth) acrylic copolymer, a formalin condensate of aromatic sulfonic acid or a salt thereof. Is preferable.
• the content of the dispersant in the dye dispersion is usually 1 to 36%, preferably 1 to 30%, more preferably 1 to 20%, still more preferably 1 to 15%.
• dispersant examples include Joncryl RTM 52J, 57J, 60J, 63J, 70J, JDX-6180, HPD-196, HPD96J, PDX-6137A, 6610, JDX-6500, JDX-6339, PDX-6102B, PDX. 6124, 67, 678, 680, 682, 683, 690 (manufactured by BASF) and the like can be mentioned, but the present invention is not limited thereto.
• the superscript RTM means a registered trademark.
• the dispersant in the dye dispersion liquid preferably has a weight average molecular weight of 1,000 to 20,000, more preferably 2,000 to 19,000, and particularly preferably 5,000 to 17,000.
• the weight average molecular weight of the styrene-acrylic acid-based copolymer is measured by the GPC (gel permission chromatograph) method.
• the acid value of the styrene- (meth) acrylic copolymer used as the dispersant is preferably 50 to 250 mgKOH / g, more preferably 100 to 250 mgKOH / g, and particularly preferably 150 to 250 mgKOH / g. preferable.
• the acid value of the resin represents the number of mg of KOH required to neutralize 1 g of the resin, and is measured according to JIS-K3054. Further, the glass transition temperature of the styrene- (meth) acrylic copolymer used as the dispersant is preferably 45 ° C. to 135 ° C., more preferably 55 ° C. to 120 ° C., and particularly preferably 60 to 110 ° C.
• styrene- (meth) acrylic copolymer which is a preferable dispersant in the above dye dispersion
• the dye dispersion can be prepared by using two or more kinds of styrene-acrylic copolymers when dispersing or dissolving the dye.
• the above dyes can be dispersed by, for example, the following method.
• a styrene-acrylic copolymer is put into a water-soluble organic solvent, the temperature is raised to 90-120 ° C. to prepare a styrene-acrylic copolymer solution, and an alkaline compound and water are put into the solution to prepare a styrene-acrylic copolymer solution.
• the formalin condensate of the aromatic sulfonic acid or a salt thereof is an anionic surfactant obtained by a condensation reaction of the aromatic sulfonic acid and formalin.
• the "salt” include salts such as sodium salt, potassium salt and lithium salt.
• the formalin condensate of aromatic sulfonic acid or a salt thereof is referred to as a formalin condensate of aromatic sulfonic acid or a salt thereof or a mixture thereof (hereinafter, unless otherwise specified, "formalin condensate of sulfonic acid”. , "The salt, or a mixture thereof" is also included) and the like are preferable.
• cleosort oil sulfonic acid cresol sulfonic acid, phenol sulfonic acid, ⁇ -naphthalene sulfonic acid, ⁇ -naphthol sulfonic acid, ⁇ -naphthalin sulfonic acid and ⁇ -naphthol sulfonic acid, benzene sulfonic acid, cresol sulfonic acid, 2-
• formalin condensates such as naphthol-6-sulfonic acid and lignin sulfonic acid.
• creosote oil sulfonic acid, ⁇ -naphthalene sulfonic acid, lignin sulfonic acid, and methylnaphthalene sulfonic acid formalin condensates are preferable. These are available as commercial products under various trade names.
• Demor N is the formal condensate of ⁇ -naphthalene sulfonic acid
• Demor C is the formal condensate of creosote oil sulfonic acid
• Demor SN-B is the formal condensate of special aromatic sulfonic acid. Kao Co., Ltd.); etc.
• Examples of the formalin condensate of creosote oil sulfonic acid include Laberin W series, and examples of the formalin condensate of methylnaphthalene sulfonic acid include Laberin AN series (both manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Among these, Demor N, Laberin AN series, and Labelin W series are preferable, Demor N and Labelin W are more preferable, and Labelin W is further preferable.
• Examples of the lignin sulfonic acid include Vanillex N, Vanillex RN, Vanillex G, Pearllex DP (all manufactured by Nippon Paper Industries, Ltd.) and the like. Among these, Vanillex RN, Vanillex N, and Vanillex G are preferable.
• the dye dispersion can further contain additives.
• the additive examples include a water-soluble organic solvent, a preservative, a surfactant, a pH adjuster, a chelating reagent, a rust preventive, a water-soluble ultraviolet absorber, a water-soluble polymer compound, a viscosity regulator, and a dye-dissolving agent. , Anti-fading agent, antioxidant, water and the like.
• water-soluble organic solvent examples include glycol solvents, polyhydric alcohols, pyrrolidones and the like.
• Glycer-based solvents include glycerin, polyglycerin (# 310, # 750, # 800,), diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, and un.
• examples thereof include compounds such as decaglycerin, dodecaglycerin, tridecaglycerin, tetradecaglycerin, and mixtures thereof.
• polyhydric alcohols examples include C2-C6 polyhydric alcohols having 2 to 3 alcoholic hydroxyl groups, di or tri-C2-C3 alkylene glycols, or poly-C2 having 4 or more repeating units and a molecular weight of about 20,000 or less.
• ⁇ C3 alkylene glycol preferably liquid polyalkylene glycol and the like.
• Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, thiodiglycol, 1,3-butanediol, 1 , 4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3 Polyhydric alcohols such as -methyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, glycerin, trimethylolpropane, 1,3-pentanediol, 1,5-pentanediol, etc.
• Examples thereof include 2-pyrrolidone and N-methyl-2-pyrrolidone, and it is preferable to contain at least either glycerin or diglycerin.
• compounds that dissolve in water and act as a wetting agent are also included in the water-soluble organic solvent in the present invention for convenience, and examples thereof include urea, ethylene urea, and saccharides.
• a solvent having a low solubility thereof is preferable, and among these, a solvent other than glycerin and a solvent other than glycerin (preferably a polyhydric alcohol other than glycerin) It is preferable to use in combination with.
• the total content of the water-soluble organic solvent in the total mass of the dye dispersion is 5 to 50%, and it is preferable to add 10 to 40%.
• preservative examples include organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, haloallyl sulfone-based, iodopropagil-based, N-haloalkylthio-based, nitrile-based, pyridine-based, 8-oxyquinolin-based, and benzo.
• the organic halogen-based compound include pentachlorophenol sodium
• specific examples of the pyridine oxide-based compound include, for example, 2-pyridinethiol-1-oxide sodium.
• isothiazolin-based compound examples include 2-pyridinethiol-1-oxide sodium.
• examples thereof include -methyl-4-isothiazolin-3-onemagnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like.
• antiseptic and fungicides include acetic anhydride, sodium sorbate or sodium benzoate, manufactured by Arch Chemical Co., Ltd., trade names Proxel RTM GXL (S), Proxel RTM XL-2 (S) and the like.
• surfactant examples include known surfactants such as anionic, cationic, nonionic, and silicone-based surfactants.
• anionic surfactants include alkyl sulfonates, alkyl carboxylates, ⁇ -olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acylamino acids and salts thereof, N-acylmethyl taurine salts, and alkyl sulfates.
• Examples of the commercially available products include, for example, High Tenor LA-10, LA-12, LA-16, Neo High Tenor ECL-30S, and ECL-45 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
• Examples of the cationic surfactant include a 2-vinylpyridine derivative and a poly4-vinylpyridine derivative.
• Examples of amphoteric surfactants include betaine lauryldimethylaminoacetate, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, betaine palm oil fatty acid amide propyldimethylaminoacetate, polyoctylpolyaminoethylglycine, and imidazoline derivatives.
• nonionic surfactant examples include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether; Esters such as polyoxyethylene oleic acid ester, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-Tetramethyl-5-decine-4,7-diol, 3,6-dimethyl-4-octin-3,6-diol, 3,5-dimethyl-1-hexin-3-ol Etc.
• ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, poly
• acetylene glycol (alcohol) type manufactured by Nisshin Kagaku Co., Ltd., trade names Surfinol 104, 105, 82, 465, orphine STG, etc .; ); Etc. can be mentioned.
• silicone-based surfactant examples include polyether-modified siloxane and polyether-modified polydimethylsiloxane. Specific examples of commercially available products include BYK-347 (polyether-modified siloxane); BYK-345, BYK-348 (polyether-modified polydimethylsiloxane), all manufactured by Big Chemie.
• fluorine-based surfactant examples include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group.
• Examples thereof include a polyoxyalkylene ether polymer compound contained in.
• Specific examples of commercially available products include, for example, Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30, FS-31 (manufactured by DuPont); PF-151N. , PF-154N (manufactured by Omniova) and the like.
• any substance can be used as long as the pH of the solution can be controlled in the range of approximately 5 to 11 without adversely affecting the prepared dye dispersion.
• alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine
• hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide
• ammonium hydroxide water ammonia
• Alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate
• alkali metal salts of organic acids such as potassium acetate
• inorganic bases such as sodium silicate and disodium phosphate, etc.
• Triethanolamine is preferred.
• chelating reagent examples include sodium ethylenediaminetetraacetate, sodium nitrilotriacetic acetate, sodium hydroxyethylethylenediamine triacetate, sodium diethylenetriamine pentaacetate, sodium uracil diacetate and the like.
• rust preventive examples include acidic sulfite, sodium thiosulfate, ammonium thioglucolate, diisopropylammonium nitrate, pentaerythritol tetranitrate, dicyclohexylammonium nitrate and the like.
• water-soluble ultraviolet absorber examples include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.
• water-soluble polymer compound examples include polyvinyl alcohol, cellulose derivatives, polyamines, polyimines, and the like.
• examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, and examples thereof include polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.
• dye-dissolving agent examples include urea, ⁇ -caprolactam, ethylene carbonate and the like.
• the above anti-fading agent is used for the purpose of improving the storage stability of images.
• various organic and metal complex-based anti-fading agents can be used.
• the organic system include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromanes, alkoxyanilines, heterocyclics and the like.
• the metal complex system include a nickel complex and a zinc complex.
• antioxidant for example, various organic and metal complex antioxidants can be used.
• organic antioxidants include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocyclics and the like. ..
• the dye dispersion liquid can contain water.
• the water that can be used is preferably one having few impurities such as ion-exchanged water and distilled water.
• the dye dispersion can be subjected to microfiltration using a membrane filter or the like.
• a membrane filter or the like When the dye dispersion is used for inkjet printing ink, it is preferable to perform microfiltration for the purpose of preventing nozzle clogging and the like.
• the pore size of the filter used for microfiltration is usually 1 ⁇ m to 0.1 ⁇ m, preferably 0.8 ⁇ m to 0.1 ⁇ m.
• the dye dispersion preferably contains at least one selected from the group consisting of a water-soluble organic solvent, a preservative, a surfactant, and a pH adjuster as the additive.
• the dye dispersion may further contain a resin emulsion.
• the resin emulsion examples include acrylic resin, epoxy resin, urethane resin, polyether resin, polyamide resin, unsaturated polyester resin, phenol resin, silicone resin, fluororesin, and polyvinyl resin (eg, polyvinyl chloride and polyvinyl acetate). , Polyvinyl alcohol, etc.), alkyd resin, polyester resin, or amino material (melamine resin, urea resin, urea resin, melamine formaldehyde resin, etc.).
• those emulsions may be composed of two or more kinds of resins. Further, it may be a composite resin in which two or more kinds of resins form a core / shell structure.
• urethane resin is preferable for use in the above dye dispersion.
• the urethane resin is often sold in the form of latex (emulsion), and most of them are emulsions having a solid content of 30 to 60%. Specific examples thereof include latex of Permarin UA-150, 200, 310, 368, 3945, Ucoat UX-320 (all manufactured by Sanyo Chemical Industries, Ltd.), Hydran WLS-201, 210, and HW-312B (above, DIC Corporation), Superflex 150, 170, 470 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the like.
• examples of the polycarbonate-based urethane resin include Permarin UA-310 and 3945, and U-coat UX-320.
• examples of the polyether urethane resin include Permarin UA-150 and 200, and U-coat UX-340. These urethane resins can be used alone or in combination.
• the urethane resin emulsion preferably has an SP value (solubility parameter) of 8 to 24, more preferably 8 to 17, and particularly preferably 8 to 11.
• SP value solubility parameter
• the SP value of the resin before neutralization is used when the emulsion is produced by neutralizing the acidic group.
• Alkaline chloride can be carried out by, for example, the following method. Examples thereof include a method in which a urethane resin emulsion having an acidic group is added to water and stirred to prepare an aqueous solution, and an alkaline compound is added to the aqueous solution to prepare a solution having a pH adjusted to 6.0-12.0.
• alkaline compound examples include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and alkaline earth metals such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide and strontium hydroxide. Examples thereof include hydroxide and triethylamine. Only one of these alkaline compounds may be used, or two or more of these alkaline compounds may be used in combination.
• the dye dispersion may be contained as a dye other than the dye represented by the formula (1), the yellow dye, and the blue dye.
• the "other dye” include "dyeing fastness test for dry heat treatment”. Method [JIS L 0879: 2005] (confirmed in 2010, revised on January 20, 2005, published by Japanese Industrial Standards Association) "," ISO 105-P01, Textiles-Tests for color fastness-PartP01: Color fastness to dr
• the dyes whose test results of the heat-sensitive heat-sensitive test (C method) contamination (polyester) in "heat (extruding pressing)” are preferably 3-4 grade or less, more preferably 3 grade or less. Among such known dyes, C.I. I. Examples of the dye having the number include the following dyes.
• yellow dye in the above other dyes examples include C.I. I. Disperse yellow dyes and C.I. I.
• solvent yellow dyes examples include those other than those exemplified as the above yellow dyes. These dyes can be used alone or in combination of two or more.
• blue dyes in the above other dyes include C.I. I. Disperse blue dyes and C.I. I.
• solvent blue dyes include those other than those exemplified as the above blue dyes. These dyes can be used alone or in combination of two or more.
• orange dye in the above other dyes examples include C.I. I. Disperse Orange 1, 1: 1, 5, 7, 11, 13, 20, 23, 25, 25: 1, 29, 33, 56, 73, 76, 113, 114, 123, 147; C.I. I. Solvent orange 60, 67 and the like can be mentioned. These dyes can be used alone or in combination of two or more.
• brown dyes in the above other dyes include C.I. I. Disperse brown 1, 3, 22, 26, 27; and the like. These dyes can be used alone or in combination of two or more.
• red dyes in the above other dyes include C.I. I. Disperse threads 4, 11, 50, 53, 55, 55: 1, 59, 60, 65, 70, 75, 92, 93, 146, 158, 190, 190: 1, 207, 239, 240, 364; C.I. I. Solvent Red 146; C.I. I. Bat Red 41; etc. These dyes can be used alone or in combination of two or more.
• Examples of the violet dye in the above other dyes include C.I. I. Disperse Violet 8, 11, 17, 23, 26, 27, 28, 29, 36, 57, 63; and the like. These dyes can be used alone or in combination of two or more.
• the dye dispersion contains at least one dye represented by the above formula (1), one or more yellow dyes, and one or more blue dyes, and the dye 1 represented by the above formula (1). It is preferable to contain one kind of the above yellow dye and two kinds of the above blue dye.
• R 1 and R 2 are independently ethyl groups
• R 3 is a hydrogen atom or a methyl group
• R 4 Contains one dye in which is a bromine atom
• the above yellow dye is C.I. I. Disperse Yellow 54
• the above blue dye is C.I. I.
• Disperse blue 60, 334, 359, 360 is preferable, and in the above formula (1), R 1 and R 2 are independently ethyl groups, R 3 is a hydrogen atom or a methyl group, and R 4 is a bromine atom. It contains one kind of dye, and the above yellow dye is C.I. I. Disperse Yellow 54, and the above blue dye is C.I. I. It is more preferable that two kinds of Disperse Blue 359 and 360 are combined.
• Each of the above dyes may be a powdery or lumpy dry coloring material, a wet cake or a slurry, and contains a small amount of a dispersant such as a surfactant for the purpose of suppressing aggregation of the coloring material particles during or after the coloring material synthesis. It may be a slurry.
• a dispersant such as a surfactant for the purpose of suppressing aggregation of the coloring material particles during or after the coloring material synthesis. It may be a slurry.
• Commercially available dyes have grades for industrial dyeing, resin coloring, ink, toner, inkjet, etc., and their manufacturing methods, purity, particle size, etc. are different from each other. In order to suppress the cohesiveness after pulverization, a color material having smaller particles is preferable, and a material having as few impurities as possible is preferable from the viewpoint of affecting dispersion stability and ink ejection accuracy.
• the dye it can be used as a color material for black by blending a yellow dye, an orange dye and a red dye mainly with a blue dye. Further, a small amount of other water-insoluble coloring material may be contained within the range of color tone adjustment.
• the present invention also includes a dye dispersion set containing the above dye dispersion and a dye dispersion having a hue different from that of the dye dispersion.
• Examples of the method for preparing the dye dispersion include a method of mixing the above components.
• the order in which the components are mixed is not particularly limited.
• the dye dispersion preferably has a viscosity at 25 ° C., which is usually about 3 to 20 mPa ⁇ s when measured with an E-type viscometer.
• the surface tension is preferably in the range of 20 to 45 mN / m when measured by the plate method. It is preferable to adjust each of these values so as to be an appropriate value in consideration of the ejection amount of the printer to be used, the response speed, the flight characteristics of the dye-dispersed droplets, and the like.
• the above-mentioned printing method for hydrophobic fibers is roughly classified into two types.
• the first method is a method called direct printing or direct printing, in which droplets of the dye dispersion are attached to hydrophobic fibers by an inkjet printer to image images such as characters and patterns.
• Step A for forming information on the hydrophobic fiber
• step B for fixing the sublimative dye in the droplet of the dye dispersion adhered by the step A to the fiber by heat, and unfixed sublimation remaining in the fiber.
• This is a method for printing hydrophobic fibers, which comprises at least three steps, step C for cleaning the sex dye.
• Step B is generally performed by known steaming or baking.
• As the steaming for example, a high temperature steamer is usually 170 to 180 ° C.
• a sublimation dye is used by a method of treating hydrophobic fibers.
• examples thereof include a method of dyeing fibers (also called moist heat fixation).
• a sublimation dye is dyed on the fibers by a method of treating the hydrophobic fibers at 190 ° C. to 210 ° C., usually about 60 seconds to 120 seconds (also called dry heat sterilization). The method can be mentioned.
• Step C is a step of washing the obtained fibers with warm water and, if necessary, water.
• the warm water or water used for cleaning may contain a surfactant.
• the second method is a method called sublimation transfer printing, sublimation transfer printing, etc., in which droplets of the dye dispersion liquid or the dye dispersion liquid set are attached to an intermediate recording medium by an inkjet printer. After obtaining recorded images such as characters and patterns, the hydrophobic fibers are brought into contact with the adhesion surface of the droplets of the dye dispersion in the intermediate recording medium and heat-treated to record the characters recorded on the intermediate recording medium.
• a method for printing hydrophobic fibers which transfers recorded images such as patterns to hydrophobic fibers.
• the sublimable dye in the dye dispersion liquid adhering to the intermediate recording medium does not aggregate on the surface and does not interfere with the sublimation of the dye when the recorded image is transferred to the hydrophobic fiber.
• An example of such an intermediate recording medium is paper in which a dye dispersion receiving layer is formed on the surface of inorganic fine particles such as silica, and special paper for inkjet can be used.
• Examples of the heat treatment for transferring the recorded image from the intermediate recording medium to the hydrophobic fiber include a dry heat treatment at about 190 to 200 ° C.
• the above printing method may further include a fiber pretreatment step for the purpose of preventing bleeding and the like.
• this pretreatment step include a step of applying an aqueous solution containing at least one or more pastes, alkaline substances, antioxidants and hydrotropy agents to the fibers before adhering the dye dispersion.
• a step of applying the pretreatment it is preferable to use an aqueous solution of the pretreatment agent containing a paste, an alkaline substance, an antioxidant and a hydrotropy agent as the pretreatment liquid, and impregnate the pretreatment liquid with fibers.
• Examples of the paste include natural gums such as guar and locust beans, starches, soda alginate, seaweeds such as furin, plant skins such as pectic acid, methyl fiber, ethyl fiber, hydroxyethyl cellulose, carboxymethyl cellulose and the like.
• Examples thereof include fibrous derivatives of the above, processed starches such as carboxymethyl starch, and synthetic glues such as polyvinyl alcohol and polyacrylic acid ester.
• Preferred is sodium alginate.
• alkaline substance examples include alkali metal salts of inorganic or organic acids, alkaline earth metal salts, and compounds that liberate alkali when heated, and include inorganic or organic alkali metal hydroxides and alkalis.
• Metal salts are preferable, and examples thereof include sodium compounds and potassium compounds. Specific examples include alkali metal hydroxides such as sodium hydroxide and calcium hydroxide, and inorganic compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, and sodium phosphate.
• Alkali metal salts of organic compounds such as sodium hydroxide, sodium trichloracetate; and the like. Preferably, sodium hydrogen carbonate is mentioned.
• the reduction inhibitor sodium metanitrobenzene sulfonate is preferable.
• the hydrotropy agent include ureas such as urea and dimethylurea, and urea is preferable.
• the paste alkaline substance, antioxidant, and hydrotropy agent, a single compound may be used, or a plurality of compounds may be used in combination.
• the mixing ratio of each pretreatment agent in the total mass of the pretreatment liquid is, for example, 0.5 to 5% for the paste, 0.5 to 5% for sodium hydrogen carbonate, and metanitrobenzene sulfonic acid on a mass basis.
• Sodium is 0-5%
• urea is 1-20%
• the rest is water.
• Examples of the application of the pretreatment agent to the cellulosic fiber include a padding method.
• the drawing ratio of the padding is preferably about 40 to 90%, more preferably about 60 to 80%.
• hydrophobic fibers include polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, polyamide fibers, and blended fibers using two or more of these fibers. Further, a blended fiber of these and a regenerated fiber such as rayon or a natural fiber such as cotton, silk and wool is also included in the hydrophobic fiber in the present specification.
• these hydrophobic fibers those having an ink receiving layer (bleeding prevention layer) are also known, and such hydrophobic fibers are also included.
• the method for forming the ink receiving layer is a known technique, and fibers having an ink receiving layer are also available as commercial products.
• the material and structure of the ink receiving layer are not particularly limited, and can be appropriately used depending on the purpose and the like.
• the dyed hydrophobic fibers obtained by the above-mentioned method for printing hydrophobic fibers are also included in the present invention.
• the dye dispersion can be used in various fields, it is suitable for water-based writing inks, water-based printing inks, information recording inks, printing, etc., and is particularly preferably used as ink for inkjet printing.
• the dye dispersion of the present invention has excellent storage stability without solid precipitation, physical property change, color change, etc. after long-term storage.
• the initial filling property to the inkjet printer head is good, and the continuous printing stability is also good. Further, it is possible to obtain a clear image without blurring of the image on the paper after printing.
• the dyed product dyed with the dye dispersion of the present invention has a high dyeing concentration, excellent leveling property and light resistance, and has a high-quality black hue. Furthermore, when used in combination with a dye dispersion containing yellow, orange, magenta, cyan dye, etc., it is possible to perform full-color inkjet printing with excellent fastness and storage stability.
• the dye dispersion liquid of the present invention is particularly suitable for inkjet printing ink because it is extremely excellent in ejection stability.
• the value of the dyeing density is 1.39 or more in the following dyeing concentration evaluation, and in the following dyeing property evaluation, no yellow bleeding or contamination is observed at the boundary between the dyed part and the white background part, and the boundary part is clear. If the color difference of 60% duty is less than 2.1 in the color rendering index 1 below and the color difference of 60% duty is less than 2.6 in the color rendering index 2 below, the dyeing is performed. It becomes a black color having a high concentration and excellent dyeability and color rendering property, and a better black printed matter can be obtained, so that it is more excellent as a dye dispersion.
• Preparation Example 1 [Preparation of emulsion] 20 parts of Joncryl 678 (manufactured by BASF) was added to 6 parts of 25% sodium hydroxide, 54 parts of ion-exchanged water, and 20 parts of propylene glycol, and the temperature was raised to 90-120 ° C. and stirred for 5 hours to obtain Joncryl 678. Emulsion solution was obtained.
• Preparation example 2 [Preparation of aqueous dispersion 1]
• a sublimation dye 30 parts of Kayaset Yellow AG (manufactured by Nippon Kayaku Co., Ltd., CI Disperse Yellow 54), 60 parts of the above Joncryl 678 emulsion, 0.2 parts of Proxel GXL, 0.4PG50 0.4 of Surfinol.
• Preparation Example 3 [Preparation of aqueous dispersion 2]
• a sublimation dye a mixture consisting of 30 parts of the following formula (2), 60 parts of the emulsion solution of Joncryl 678, 0.2 parts of Proxel GXL, 0.4 parts of Surfinol 104PG50, and 24 parts of ion-exchanged water was added in 0.2 mm.
• the dispersion treatment was carried out for about 15 hours under cooling in a sand mill using diameter glass beads.
• Preparation Example 4 [Preparation of aqueous dispersion 3]
• a sublimation dye a mixture consisting of 30 parts of the following formula (3), 60 parts of the emulsion solution of Joncryl 678, 0.2 parts of Proxel GXL, 0.4 parts of Surfinol 104PG50, and 24 parts of ion-exchanged water was added in 0.2 mm.
• the dispersion treatment was carried out for about 15 hours under cooling in a sand mill using diameter glass beads.
• Preparation Example 5 [Preparation of aqueous dispersion 4]
• a sublimation dye C.I. I. A mixture consisting of 30 parts of Disperse Blue 359, 60 parts of the above Joncryl 678 emulsion, 0.2 parts of Proxel GXL, 0.4 parts of Surfinol 104PG50, and 24 parts of ion-exchanged water was prepared using 0.2 mm diameter glass beads. The dispersion treatment was carried out in a sand mill for about 15 hours under cooling.
• Preparation Example 6 [Preparation of aqueous dispersion 5]
• a sublimation dye C.I. I. A mixture consisting of 30 parts of Disperse Blue 360, 60 parts of the above Joncryl 678 emulsion, 0.2 parts of Proxel GXL, 0.4 parts of Surfinol 104PG50, and 24 parts of ion-exchanged water was prepared using 0.2 mm diameter glass beads. The dispersion treatment was carried out in a sand mill for about 15 hours under cooling.
• Preparation Example 8 [Preparation of aqueous dispersion 7]
• a sublimation dye C.I. I. A mixture consisting of 30 parts of Disperse Brown 27, 60 parts of the above Joncryl 678 emulsion, 0.2 parts of Proxel GXL, 0.4 parts of Surfinol 104PG50, and 24 parts of ion-exchanged water was prepared using 0.2 mm diameter glass beads. The dispersion treatment was carried out in a sand mill for about 15 hours under cooling.
• Preparation Example 9 [Preparation of aqueous dispersion 8]
• a sublimation dye C.I. I. A mixture consisting of 30 parts of Disperse Orange 25, 60 parts of the above Joncryl 678 emulsion, 0.2 parts of Proxel GXL, 0.4 parts of Surfinol 104PG50, and 24 parts of ion-exchanged water was prepared using 0.2 mm diameter glass beads. The dispersion treatment was carried out in a sand mill for about 15 hours under cooling.
• Example 2 In Example 1, the aqueous black dye dispersion of Example 2 is the same as in Example 1 except that the aqueous dispersion 3 obtained in Preparation Example 4 is added instead of the aqueous dispersion 2 as shown in Table 1.
• aqueous dispersion 6 Twenty-three parts of the obtained aqueous dispersion 6 was mixed, and glycerin, Proxel GXL (manufactured by Ronza), Surfinol 465 (manufactured by Nisshin Chemical Industry Co., Ltd.), TEA-80 (manufactured by Genuine Chemical Co., Ltd.), And ion-exchanged water were added to have the compositions shown in Table 1 and stirred, and then filtered through a 5 ⁇ m filter to obtain an aqueous black dye dispersion of Comparative Example 4.
• glycerin, Proxel GXL manufactured by Ronza
• Surfinol 465 manufactured by Nisshin Chemical Industry Co., Ltd.
• TEA-80 manufactured by Genuine Chemical Co., Ltd.
• the aqueous black dye dispersions of Examples 1 and 2 have better color rendering properties, higher dyeing concentration, and higher quality than the aqueous black dye dispersions of Comparative Examples 1 to 4. It shows a black color, and it can be seen that it is also excellent in the uniformity of sublimation transfer (uniform dyeing property) and light resistance.
• the dye dispersion liquid containing at least one type of dye represented by the formula (1) according to the present invention, at least one type of yellow dye, and at least one type of blue dye is a transfer paper having a low basis weight. It is extremely useful as various recording inks, especially ink for inkjet printing, because it is possible to obtain dyed products with excellent color tones with high transfer efficiency and high dyeing density even when transfer paper with a small ink receiving layer is used. Is shown.
• the dye dispersion of the present invention has high sublimation transfer efficiency and a high dyeing concentration can be obtained.

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