JP7332262B2 - Dispersion composition for ink - Google Patents

Description

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain an ink dispersion composition and an ink composition which are extremely excellent in light resistance.

As the digitization of information progresses, inkjet printing is widely used as a printing machine for office and home use. Along with the spread of inkjet printing applications, various coloring materials are used depending on the application, from water-soluble dyes such as conventional acid dyes and direct dyes to water-insoluble coloring materials such as disperse dyes and pigments. It's starting to be done. On the other hand, disperse dyes are widely used for industrial dyeing of hydrophobic fibers such as polyester, and are used for dyeing by dispersing water-insoluble dyes in a dye bath or color paste. Under high-temperature conditions, the dye permeates and diffuses into the fibers in a dispersed state, and is dyed by hydrogen bonding and intermolecular forces between the fiber dyes. In addition, inkjet printing of polyester fibers using disperse dyes has also been performed (Non-Patent Document 1, Non-Patent Document 2). and a thermal transfer printing method in which dye ink is applied (printed) to a special transfer paper and then the dye is sublimated and transferred from the transfer paper side to the fiber side by heat.

In the future, in order to expand the application field of printing methods using ink, the ink composition used for inkjet recording and the colored body colored by it have high color development and various fastnesses such as light resistance and water resistance. is required to be good. Therefore, when used as an ink composition, there is a demand for the development of an ink composition that has good fastness properties, high density of images obtained by printing, and good storage stability. The current situation is that there are few things to have.
In particular, common blue dyes used for dyeing polyester fibers include C.I. I. Disperse Blue 359 can be mentioned. Since this dye does not have high light resistance, the development of a dye having high light resistance is strongly demanded from the market. However, at present, no dyes have been found that can satisfy this requirement.

JP-A-8-34941 JP-A-10-158555 Japanese Patent No. 5911057 Japanese Patent No. 6219333 Japanese Patent No. 4016483 Japanese Patent No. 4078679 WO2010/013651 Japanese Patent No. 2675956 Japanese Patent No. 3839829 WO2014/129322 WO2013/115071 Japanese Patent Application Laid-Open No. 2018-119022 Japanese Patent Laid-Open No. 2015-63586 Japanese Patent No. 4406093 Japanese Patent No. 3454024 Japanese Patent No. 4030368

Journal of the Imaging Society of Japan Vol.41 No.2 p68-74 (2002) Textile Economics Newspaper, January 28, 2004, pp. 18-21 Revised 4th Edition Chemical Engineering Dictionary pp.46-47 DIC Technical Review No. 10/2004

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and to provide a colored liquid that exhibits good light resistance even when used as an ink composition.

As a result of intensive studies to solve the above problems, the present inventors have found that a compound represented by the following formula (1) and C.I. I. Disperse Blue 359 was found to have high lightfastness.

That is, the present invention relates to the following 1) to 15).
1)
a compound represented by the following formula (1); I. A coloring liquid containing Disperse Blue 359.

(In the formula, X ₁ to X ₅ each independently represent a group selected from the group consisting of a hydrogen atom, an amino group and a hydroxy group.)
2)
The compound represented by the above formula (1) is C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 81, C.I. I. Disperse Blue 97, C.I. I. The coloring liquid according to 1), which is at least one selected from the group consisting of Disperse Blue 145.
3)
C.I. I. The content of Disperse Blue 359 and the content of the compound represented by the above formula (1) is the content weight ratio (C.I. Disperse Blue 359 and the compound represented by the above formula (1) The coloring liquid according to 1) or 2), wherein the ratio) is in the range of 1:0.3 to 1:4.0.
4)
The colored liquid according to any one of 1) to 3), further comprising a dispersant.
5)
The colored liquid according to 4), wherein the dispersant is at least one dispersant selected from the group consisting of anionic dispersants, nonionic dispersants, and polymeric dispersants.
6)
The above anionic dispersant is at least one selected from the group consisting of a formalin condensate of β-naphthalenesulfonate, a formalin condensate of alkylnaphthalenesulfonate, and a formalin condensate of creosote oil sulfonate 5) The coloring liquid described in .
7)
The colored liquid according to 5) or 6), further comprising at least one selected from the group consisting of phytosterol compounds and cholestanol compounds.
8)
The colored liquid according to any one of 5) to 7), wherein the polymeric dispersant comprises a styrene/acrylic polymer dispersant.
9)
The colored liquid according to any one of 1) to 8), further comprising an antifoaming agent.
10)
The colored liquid according to any one of 1) to 9), further comprising a water-soluble organic solvent.
11)
The colored liquid according to any one of 1) to 10), further comprising a preservative.
12)
The colored liquid according to any one of 1) to 11), further comprising a rosin compound.
13)
The compound represented by the above formula (1) and the above C.I. I. The colored liquid according to any one of 1) to 12), wherein Disperse Blue 359 forms particles having a number average particle diameter of 10 to 500 nm in the colored liquid.
14)
An inkjet ink containing the coloring liquid according to any one of 1) to 13), an inkjet printing method and an inkjet printed matter using the inkjet ink.
15)
14) A sublimation transfer dyeing method and a sublimation transfer dyed material, wherein the ink-jet printed material according to 14) is heated to sublimate-transfer the coloring material applied to the printed material side to an object to be dyed.

INDUSTRIAL APPLICABILITY According to the present invention, a coloring liquid having extremely excellent light resistance and an inkjet ink using the same can be obtained. In the specification of the present application, the inkjet ink may be simply abbreviated as ink.

The coloring liquid contains the compound represented by the above formula (1) and C.I. I. Disperse Blue 359 and

In formula (1) above, X ₁ to X ₅ each independently represent a group selected from the group consisting of a hydrogen atom, an amino group and a hydroxy group, and at least two of X ₁ to X ₄ are hydroxy groups. , and the other two are amino groups or hydrogen atoms, preferably one of X ₁ and X ₃ is an amino group and the other is a hydroxy group, and one of X ₂ and X ₄ is an amino group and the other is a hydroxy group is more preferred.

Examples of the compound represented by formula (1) include dyes and pigments.

Examples of the above-mentioned dyes include organic dyes that dye fibers by an appropriate dyeing method. Specifically, disperse dyes, oil-soluble dyes, etc. are preferably used, and disperse dyes C.I. I. Disperse Blue 56, 81, 97, 145 and the like can be mentioned, but are not limited to these. The ink dispersion composition preferably contains at least one selected from these disperse dyes, but may contain two or more disperse dyes.

The compound represented by the above formula (1) may be a powdery or lumpy dry colorant, a wet cake or a slurry. It may be contained. Commercially available compounds represented by the above formula (1) include grades for industrial dyeing, resin coloring, ink, toner, inkjet, etc., and the manufacturing method, purity, pigment particle size, etc. are different. . In order to suppress aggregation after pulverization, smaller particles are preferable, and particles containing as few impurities as possible are preferable from the viewpoint of the influence on the dispersion stability and ejection accuracy of the coloring liquid or ink. The above dye can be used as a black ink by blending an orange dye and a red dye with a blue dye as a main component. Further, a small amount of a coloring component other than the compound represented by the above formula (1) may be included within the range of color tone adjustment.

Two or more kinds of the above dyes may be blended. For example, in the preparation of black ink, a blue dye is mainly blended with an orange dye and a red dye to obtain a black color, and this is used as a black dye. can be used. Further, for example, a plurality of dyes may be blended for the purpose of finely adjusting the color tone of blue, orange, red, violet, black, or the like to a more preferred color tone.

The content of the compound represented by the formula (1) in the colored liquid is not particularly limited, but the total amount of the compound represented by the formula (1) is equal to the total amount of the colored liquid. 0.1 to 25% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight. If the amount of the compound represented by the above formula (1) is less than 0.1% by weight, the color density will be insufficient. On the other hand, when the content exceeds 25% by weight, the storage stability of the ink dispersion composition tends to be poor.

[C. I. About Disperse Blue 359]
C. above. I. The content of Disperse Blue 359 in the coloring liquid is not particularly limited, but is 0.1 to 25% by weight, preferably 0.5 to 20% by weight, based on the total amount of the coloring liquid. , more preferably in the range of 1 to 15% by weight. C. I. If the content of Disperse Blue 359 is less than 0.1% by weight, the density of color development will be insufficient. On the other hand, when the content exceeds 25% by weight, the storage stability of the ink dispersion composition tends to be poor.

A compound represented by the above formula (1) and C.I. I. The total content of Disperse Blue 359 is in the range of 0.2 to 50% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, relative to the total amount of the coloring liquid. .

C. above. I. The weight ratio of the content of Disperse Blue 359 and the content of the compound represented by the above formula (1) is preferably in the range of 1:0.3 to 1:4.0, preferably 1:1. More preferably, it is in the range of ~1:2.3.

[About dispersant]
The coloring liquid can contain a dispersant. The dispersant is preferably, for example, at least one dispersant selected from the group consisting of anionic dispersants, nonionic dispersants, and polymeric dispersants.

Examples of the anionic dispersant include polymeric sulfonic acid, formalin condensate of aromatic sulfonic acid, ligninsulfonic acid, formalin condensate of ligninsulfonic acid, salts thereof, or mixtures thereof (hereinafter, particularly Unless otherwise specified, the term "formalin condensate of sulfonic acid" is meant to include "these salts or mixtures thereof".), formalin condensates of alkylnaphthalenesulfonates and the like are preferred. "These salts" include salts such as sodium salts, potassium salts and lithium salts. Examples of formalin condensates of aromatic sulfonic acids include creosote oil sulfonic acid; cresol sulfonic acid; phenolsulfonic acid; β-naphthalenesulfonic acid; β-naphtholsulfonic acid; cresolsulfonic acid and 2-naphthol-6-sulfonic acid; ligninsulfonic acid; and formalin condensates. Among these, formalin condensates of creosote oil sulfonic acid; β-naphthalene sulfonic acid; lignin sulfonic acid; are preferred. These are commercially available under various trade names. Examples include Demol N as a formalin condensate of β-naphthalenesulfonic acid; Demol C as a formalin condensate of creosote oil sulfonic acid; and Demol SN-B as a formalin condensate of a special aromatic sulfonic acid. manufactured by Kao Corporation); Examples of formalin condensates of creosote oil sulfonic acid include Labelin W series; examples of formalin condensates of methylnaphthalene sulfonic acid include Labelin AN series (both manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.); Among these, Demoll N, Labellin AN series, and Labellin W series are preferred, Demoll N and Labellin W are more preferred, and Labellin W is even more preferred. Examples of ligninsulfonic acid include Vanilex N, Vanilex RN, Vanilex G, and Pearllex DP (all manufactured by Nippon Paper Industries Co., Ltd.). Among these, Vanilex RN, Vanilex N, and Vanilex G are preferred.

Examples of the nonionic dispersant include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and the like. Ether type; polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, etc. Ester type; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne- Acetylene glycol (alcohol) system such as 3-ol; manufactured by Nissin Kagaku Co., Ltd., product names Surfynol 104, 105, 82, 465, Olphine STG, etc.; polyglycol ether system (eg Tergitol 15-S manufactured by SIGMA-ALDRICH) -7 etc.); Of these, acetylene glycol-based antifoaming agents are preferred, and Surfynol 104, 105, 82 and 465 (trade names, manufactured by Nissin Kagaku Co., Ltd.) are more preferred.

As the polymer-based dispersant, for example, those commonly used in inkjet inks and the like are preferable, and a copolymer polymer having a hydrophilic portion and a hydrophobic portion in the molecule, specifically an acrylic acid-based dispersant agents such as styrene-acrylic acid copolymers, styrene-acrylic acid-acrylic acid ester copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, and other styrene-acrylic polymers Dispersants or maleic acid-based dispersants, such as styrene-maleic acid copolymers, acrylate-maleic acid copolymers, styrene-acrylate-maleic acid copolymers, sulfonic acid-based dispersants, such as Acrylic acid ester-styrenesulfonic acid copolymer, styrene-methacrylsulfonic acid copolymer, acrylic acid ester-allylsulfonic acid copolymer, polyester dispersants such as polyester-acrylic acid copolymer, polyester-acrylic acid- Known polymeric dispersants such as acrylic ester copolymers, polyester-methacrylic acid copolymers, polyester-methacrylic acid-acrylic acid ester copolymers, and salts thereof can be used. These can be obtained as commercial products, for example, Joncryl 67 (trade name, manufactured by BASF Japan Ltd.), Joncryl 678 (trade name, manufactured by BASF Japan Ltd.), Joncryl 586 (trade name, manufactured by BASF Japan Ltd.) Co., Ltd.), Joncryl 611 (trade name, manufactured by BASF Japan Ltd.), Joncryl 680 (trade name, manufactured by BASF Japan Ltd.), Joncryl 682 (trade name, manufactured by BASF Japan Ltd.), Joncryl 683 (trade name, manufactured by BASF Japan Ltd.), Joncryl 690 (trade name, manufactured by BASF Japan Ltd.), and the like. In this specification, "(meth)acryl" means "acryl" and/or "methacryl".

The styrene-(meth)acrylic copolymer is a copolymer of a styrene-based monomer and a (meth)acrylic-based monomer. Specific examples of these copolymers include (α-methyl)styrene-acrylic acid copolymer, (α-methyl)styrene-acrylic acid-acrylate copolymer, (α-methyl)styrene- Methacrylic acid copolymer, (α-methyl)styrene-methacrylic acid-acrylate copolymer, (α-methyl)styrene-(anhydride) maleic acid copolymer, acrylic ester-(anhydride) maleic acid copolymer coalescence, (α-methyl)styrene-acrylate-(anhydride) maleic acid maleic acid copolymer, acrylic ester-allylsulfonic acid ester copolymer, acrylic ester-styrenesulfonic acid copolymer, (α- methyl)styrene-methacrylsulfonic acid copolymer, polyester-acrylic acid copolymer, polyester-acrylic acid-acrylic acid ester copolymer, polyester-methacrylic acid copolymer, polyester-methacrylic acid-acrylic acid copolymer ester ; and the like. Among these, styrene is preferred as the compound containing an aromatic hydrocarbon group.
The term (α-methyl)styrene is used herein to include α-methylstyrene and styrene. Specific examples include Joncryl ^RTM 52J, 57J, 60J, 63J, 70J, JDX-6180, HPD-196, HPD96J, PDX-6137A, 6610, JDX-6500, JDX-6639, PDX-6102B, PDX-6124 (BASF (manufactured), etc., but are not limited to these. In this specification, the superscript RTM means a registered trademark.

From the standpoint of dispersion stability as the coloring liquid or ink, the dispersant, together with an anionic dispersant, a nonionic dispersant, and a polymeric dispersant, is an ethylene oxide adduct of phytosterols, and cholestanols. can be used in combination with known nonionic dispersants such as ethylene oxide adducts of

The phytosterols include either phytosterols or hydrogenated phytosterols. For example, ethylene oxide adducts of phytosterols include ethylene oxide adducts of phytosterols and ethylene oxide adducts of hydrogenated phytosterols. can. The cholestanols include both cholestanols and hydrogenated cholestanols. For example, the ethylene oxide adduct of cholestanol is an ethylene oxide adduct of cholestanol or ethylene Mention may be made of oxide adducts. The addition amount of ethylene oxide per mol of phytosterols or cholestanols is about 10 to 50 mol, and the HLB is preferably about 13 to 20. Examples of phytosterol ethylene oxide adducts include NIKKOL BPS-20 and NIKKOL BPS-30 (both manufactured by Nikko Chemicals Co., Ltd., EO adducts of phytosterols), NIKKOL BPSH-25 (same, EO adducts of hydrogenated phytosterols), and the like. available on the market as Ethylene oxide adducts of cholestanols are commercially available as, for example, NIKKOL DHC-30 (EO adduct of cholestanol).

The dispersant may further contain a cationic dispersant and/or an amphoteric dispersant.
Examples of the cationic dispersant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts. Examples of the amphoteric dispersant include carboxybetaines, sulfobetaines, aminocarboxylates, imidazolinium betaine, and the like.

The dispersant preferably has a weight average molecular weight of 1,000 to 20,000, more preferably 2,000 to 19,000, and particularly preferably 4,000 to 17,000. If the weight-average molecular weight is too small, the ability to stabilize the dispersion of the water-insoluble colorant will be reduced. I don't like it. The weight average molecular weight of the styrene-(meth)acrylic acid copolymer can be measured by GPC (gel permeation chromatography). 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°C to 110°C. Furthermore, the oxidation of the styrene-(meth)acrylic copolymer used as a dispersant is preferably 50 to 250 mgKOH/g, more preferably 100 to 250 mgKOH/g, particularly preferably 150 to 250 mgKOH/g. . If the acid value is too small, the solubility of the resin in water tends to be poor, and the ability to stabilize the dispersion of water-insoluble colorants tends to be poor. , there is a tendency that the printed image tends to bleed, which is not preferable. The acid value of a resin represents the number of mg of KOH required to neutralize 1 g of resin, and can be measured according to JIS-K3054.

As the dispersant, a styrene-(meth)acrylic copolymer is preferable, and specific examples thereof include Joncryl 67 (weight average molecular weight = 12,500, acid value = 213), 678 (weight average molecular weight = 8 , 500, acid value = 215), 682 (weight average molecular weight = 17,00, acid value = 230), 683 (weight average molecular weight = 4,900, acid value = 215), 690 (weight average molecular weight = 16,500 , acid value = 240) and the like.

Dispersants other than the above include, for example, styrene and derivatives thereof, vinylnaphthalene and derivatives thereof, aliphatic alcohol esters of α,β-ethylenically unsaturated carboxylic acids, acrylic acid and derivatives thereof, maleic acid and derivatives thereof, At least two monomers selected from itaconic acid and its derivatives, fumaric acid and its derivatives, vinyl acetate, vinyl alcohol, vinylpyrrolidone, acrylamide, and derivatives thereof, at least one of which is hydrophilic or water-soluble monomers), random copolymers and graft copolymers, and/or salts thereof.

The total amount of the dispersant is preferably 1 to 120% by mass, more preferably 10 to 100% by mass, and still more preferably 20 to 80% by mass, relative to the total amount of the compound represented by the formula (1). % by mass.

The coloring liquid may further contain an antifoaming agent. The antifoaming agent is a substance that has the effect of reducing foam in a solution or suppressing foaming itself. is mentioned. Specific examples include highly oxidized oil-based, glycerin fatty acid ester-based, fluorine-based, and silicone-based compounds.

The coloring liquid may further contain a water-soluble organic solvent.
Specific examples of water-soluble organic solvents include (C1-C4) alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol; N,N-dimethylformamide, N, carboxylic acid amides such as N-dimethylacetamide; lactams such as 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidine-2 -one, cyclic ureas such as 1,3-dimethylhexahydropyrimid-2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; tetrahydrofuran, dioxane, etc. cyclic ethers of; ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetra mono-, oligo- or polyalkylene glycols or thioglycols having C2-C6 alkylene units such as ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, dithiodiglycol; trimethylolpropane, glycerin, hexane-1 , 2,6-triol (preferably triol); ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol) triethylene glycol monomethyl ether, triol (C1-C4) alkyl ethers of polyhydric alcohols such as ethylene glycol monoethyl ether; γ-butyrolactone; dimethyl sulfoxide; These organic solvents may be used alone or in combination of two or more. The above water-soluble organic solvents include substances that are solid at room temperature, such as trimethylolpropane. Since it can be used for the same purpose as the water-soluble organic solvent, it is described in the category of the water-soluble organic solvent in this specification for convenience.

The coloring liquid may further contain a preservative.
Examples of antiseptics include organic sulfur, organic nitrogen sulfur, organic halogen, haloallyl sulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, and benzothiazole. type, isothiazoline type, dithiol type, pyridine oxide type, nitropropane type, organic tin type, phenol type, quaternary ammonium salt type, triazine type, thiazine type, anilide type, adamantane type, dithiocarbamate type, brominated indanone type, Compounds such as benzyl bromoacetate-based compounds and inorganic salt-based compounds are included. Specific examples of organic halogen compounds include sodium pentachlorophenol, specific examples of pyridine oxide compounds include 2-pyridinethiol-1-oxide sodium, and specific examples of isothiazoline compounds. is, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2 -methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like. Specific examples of other preservatives include anhydrous sodium acetate, sodium sorbate or sodium benzoate, product names Proxel ^RTM GXL (S) and Proxel ^RTM XL-2 (S) manufactured by Arch Chemicals.

The coloring liquid may further contain a rosin compound. Rosin is generally a resin component collected from rosin, and the components and proportions contained differ depending on the collection method. Representative examples of rosins include gum rosin, tall rosin and wood rosin. The rosin-based compound contained in the colored liquid of the present invention includes, for example, abietic acid, abietic acid salt, dihydroabietic acid, dihydroabietic acid salt, neoabietic acid, neoabietic acid salt, dehydroabietic acid, dehydroabietic acid. Acid salts, tetrahydroabietic acid, salts of tetrahydroabietic acid, palustric acid, salts of palustric acid, levopimaric acid, salts of levopimaric acid, pimaric acid, salts of pimaric acid, isopimaric acid, salts of isopimaric acid, citronellic acid , salts of citronellic acid, polymerized rosin, salts of polymerized rosin, rosin esters, and salts of rosin esters. In addition, the rosin-based compound can be obtained as ^a commercial product. series (R-140, R-95, etc.), Super Ester E788, Super Ester E722, Estergum AA-G, Pencel GA100.

The coloring liquid may further contain ink preparation agents such as pH adjusters, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, pigment solubilizers, antioxidants, and surfactants. good.

The compound represented by the above formula (1) and the above C.I. I. Disperse Blue 359 preferably forms particles having a number average particle diameter of 10 to 500 nm in the coloring liquid. The number average particle diameter of the particles is preferably 10 to 500 nm, more preferably 10 to 300 nm. Also, the maximum particle size is preferably 900 nm or less. When the number average particle size and the maximum particle size are large, clogging tends to occur and stable ejection becomes impossible in the ink jet textile printing method in which fine nozzles are used for ejection, which is not preferable. If the number average particle size exceeds 500 nm, it tends to be difficult to stably eject the ink composition. In addition, when the number average particle diameter is 10 nm or less, the particles tend to agglomerate and sedimentation, which tends to clog nozzles and filters. The number-average particle size can be determined by a commercially available particle size analyzer using a light scattering method, an electrophoresis method, a laser Doppler method, or the like.

The above colored liquid is extremely excellent in storage stability. Therefore, when the colored liquid is used as an ink, excellent ejection stability can also be achieved. In particular, when the aqueous inkjet ink is used, the dye and/or pigment may be contained as a coloring component in the aqueous inkjet ink in an amount of 0.3 to 10% by mass based on the total amount of the aqueous inkjet ink. preferable. In addition, the above preservatives, pH adjusters, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, pigment solubilizers, antioxidants, surfactants, etc. are added to make water-based inkjet inks. can be

As the pH adjuster, any substance can be used as long as it can control the pH of the ink in the range of 5 to 11 without adversely affecting the prepared ink. Specific examples thereof include alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water). , alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate and potassium carbonate; alkali metal salts of organic acids such as potassium acetate; inorganic bases such as sodium silicate and disodium phosphate.

Specific examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracil diacetate.

Examples of the rust preventive include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate and dicyclohexylammonium nitrite.

Examples of the water-soluble ultraviolet absorbent include sulfonated benzophenone-based compounds, benzotriazole-based compounds, salicylic acid-based compounds, cinnamic acid-based compounds, and triazine-based compounds.

Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines and polyimine.

Examples of the viscosity modifier include water-soluble organic solvents as well as water-soluble polymer compounds such as polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.

Examples of the dye-dissolving agent include urea, ε-caprolactam, and ethylene carbonate.

The anti-fading agent is used for the purpose of improving the storability of images. As the antifading agent, various organic and metal complex antifading agents can be used. Organic compounds include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of metal complexes include nickel complexes and zinc complexes.

As the antioxidant, for example, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocyclics, and the like. .

Examples of the surfactant include known surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and silicone surfactants.

Examples of the anionic surfactant include alkylsulfonates, alkylcarboxylates, α-olefinsulfonates, polyoxyethylene alkyl ether acetates, N-acylamino acids and their salts, N-acylmethyltaurate salts, Alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate, lauryl alcohol sulfate, alkylphenol type phosphate, alkyl type phosphate, alkylaryl sulfone acid salt, diethylsulfosuccinate, diethylhexylsulfosuccinate, dioctylsulfosuccinate, and the like. Specific examples of the commercially available products include Hitenol LA-10, LA-12, LA-16, Neohitenol ECL-30S and ECL-45, all of which are all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

Examples of cationic surfactants include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

Examples of the amphoteric surfactant include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, imidazoline derivatives and the like.

Examples of the nonionic surfactant include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and the like. Ether type; polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, etc. Ester type; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne- Acetylene glycol (alcohol) system such as 3-ol; manufactured by Nissin Kagaku Co., Ltd., product names Surfynol 104, 105, 82, 465, Olphine STG, etc.; polyglycol ether system (eg Tergitol 15-S manufactured by SIGMA-ALDRICH) -7 etc.);

Examples of the silicone surfactant include polyether-modified siloxane and polyether-modified polydimethylsiloxane. Specific examples of commercially available products include BYK-347 (polyether-modified siloxane); BYK-345 and BYK-348 (polyether-modified polydimethylsiloxane), all of which are manufactured by BYK-Chemie. Examples of fluorine-based surfactants include perfluoroalkylsulfonic acid compounds, perfluoroalkylcarboxylic acid compounds, perfluoroalkylphosphoric acid ester compounds, perfluoroalkylethylene oxide adducts, and perfluoroalkyl ether groups having side chains. and polyoxyalkylene ether polymer compounds having Specific examples of commercially available products include 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 Omnova), and the like.

Each of the above ink preparation agents can be used alone or in combination.

The coloring liquid may contain water. As the water that can be contained, water containing few impurities, such as ion-exchanged water and distilled water, is preferable. Further, the ink prepared using the above coloring liquid can be subjected to precision filtration using a membrane filter or the like. When the above ink is used as an inkjet ink, it is preferable to perform microfiltration for the purpose of preventing clogging of nozzles. The pore size of the filter used for microfiltration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

[Method for producing colored liquid]
As the method for producing the colored liquid of the present invention, the following two production methods can be mainly used, but the method is not limited to these.

The first manufacturing method includes the following manufacturing method.

Specifically, the compound represented by the above formula (1), and C.I. I. It is carried out by mixing and dispersing a solution containing Disperse Blue 359, water, an antifoaming agent, a dispersing agent and a preservative.

More specifically, the compound represented by the above formula (1), and C.I. I. Glass beads are added to a solution containing Disperse Blue 359, water, an antifoaming agent, a dispersing agent and a preservative, and the mixture is dispersed using a sand mill under water cooling for about 15 hours. For this dispersion treatment, in addition to the sand mill (bead mill), for example, a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, etc. are used to stir and mix each component constituting the dispersion. It is possible to use the method of Although the dispersion time is not particularly limited, the compound represented by the above formula (1) and C.I. I. It is preferable to set the number average particle diameter of the particles containing Disperse Blue 359 to 10 to 500 nm. By setting the number average particle diameter to be 10 to 500 nm, deterioration of the dispersion stability and storage stability of the coloring liquid or ink can be prevented. Foaming may occur during the above dispersion treatment, but in such a case, this can be suppressed by adding an ink preparation agent such as a water-soluble organic solvent or a surfactant. Further, if necessary, a silicone antifoaming agent, an acetylene alcohol antifoaming agent, or the like may be added during preparation of the dispersion. However, since some antifoaming agents inhibit the dispersion and microparticulation of dyes and the like, it is preferable to use an antifoaming agent that does not affect the microparticulation and the stability of the dispersion. Preferred antifoaming agents include, for example, Olphine series (SK-14, etc.) manufactured by Nissin Chemical Industry Co., Ltd.; Surfynol series (104, DF-110D, etc.) manufactured by Air Products Japan Co., Ltd.; . Further, the dispersion was filtered through glass fiber filter paper GC-50 (manufactured by Toyo Roshi Kaisha, Ltd., filter pore size 0.5 μm) to obtain an aqueous dispersion from which components with large particle sizes were removed. For the purpose of controlling the number average particle size, the above glass beads may have any particle size.

The second manufacturing method includes the following manufacturing method.

Specifically, it is a method of preparing two kinds of dispersion liquids and mixing them to produce a colored liquid.

<First dispersion preparation step>
As a method for producing the first dispersion, for example, the following production method can be used. Specifically, glass beads are added to a solution containing the compound represented by the above formula (1), water, an antifoaming agent, a dispersant, and a preservative, and a sand mill is used to perform dispersion treatment under water cooling for about 15 hours. . For this dispersion treatment, in addition to the sand mill (bead mill), for example, a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, etc. are used to stir and mix each component constituting the dispersion. It is possible to use the method of Although the dispersion time is not particularly limited, it is preferably set so that the compound represented by the above formula (1) has a number average particle diameter of 10 to 500 nm. By setting the number average particle diameter to be 10 to 500 nm, deterioration of the dispersion stability and storage stability of the coloring liquid or ink can be prevented. Foaming may occur during the above dispersion treatment, but in such a case, this can be suppressed by adding an ink preparation agent such as a water-soluble organic solvent or a surfactant. Further, if necessary, a silicone antifoaming agent, an acetylene alcohol antifoaming agent, or the like may be added during preparation of the dispersion. However, since some antifoaming agents inhibit the dispersion and microparticulation of dyes and the like, it is preferable to use an antifoaming agent that does not affect the microparticulation and the stability of the dispersion. Preferred antifoaming agents include, for example, Olphine series (SK-14, etc.) manufactured by Nissin Chemical Industry Co., Ltd.; Surfynol series (104, DF-110D, etc.) manufactured by Air Products Japan Co., Ltd.; . Then, the dispersion was filtered through glass fiber filter paper GC-50 (manufactured by Toyo Roshi Kaisha, Ltd., filter pore size 0.5 μm) to obtain an aqueous dispersion from which components with large particle sizes were removed. For the purpose of controlling the number average particle size, the above glass beads may have any particle size.

<Second dispersion preparation step>
As a method for producing the second dispersion, for example, the following production method can be used. Specifically, C.I. I. Glass beads are added to a solution containing Disperse Blue 359, water, an antifoaming agent, a dispersing agent and an antiseptic, and the mixture is dispersed using a sand mill under water cooling for about 15 hours. For this dispersion treatment, in addition to the sand mill (bead mill), for example, a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, etc. are used to stir and mix each component constituting the dispersion. It is possible to use the method of Although the dispersion time is not particularly limited, C.I. I. It is preferable to set the number average particle size of Disperse Blue 359 to 10 to 500 nm. By setting the number average particle diameter to be 10 to 500 nm, deterioration of the dispersion stability and storage stability of the coloring liquid or ink can be prevented. Foaming may occur during the above dispersion treatment, but in such a case, this can be suppressed by adding an ink preparation agent such as a water-soluble organic solvent or a surfactant. Further, if necessary, a silicone antifoaming agent, an acetylene alcohol antifoaming agent, or the like may be added during preparation of the dispersion. However, since some antifoaming agents inhibit the dispersion and microparticulation of dyes and the like, it is preferable to use an antifoaming agent that does not affect the microparticulation and the stability of the dispersion. Preferred antifoaming agents include, for example, Olphine series (SK-14, etc.) manufactured by Nissin Chemical Industry Co., Ltd.; Surfynol series (104, DF-110D, etc.) manufactured by Air Products Japan Co., Ltd.; . Further, the dispersion was filtered through glass fiber filter paper GC-50 (manufactured by Toyo Roshi Kaisha, Ltd., filter pore size 0.5 μm) to obtain an aqueous dispersion from which components with large particle sizes were removed. For the purpose of controlling the number average particle size, the above glass beads may have any particle size.

<Dispersion mixing step>
The colored liquid of the present invention is prepared by mixing the first dispersion and the second dispersion. Examples of the method of mixing the dispersions include a method of mixing the two dispersions while stirring to prepare a colored liquid.

An inkjet ink containing the coloring liquid is also included in the present invention.

Examples of the method for preparing the inkjet ink include a method of adding and mixing a water-soluble organic solvent and, if necessary, an ink preparation agent to the coloring liquid. The order in which these are mixed is not particularly limited. These ink preparation agents may be added as long as they do not impair the effects of the present invention.

The pH of the inkjet ink is preferably pH 5 to 11, more preferably pH 7 to 10, for the purpose of improving storage stability. The pH and surface tension of the inkjet ink can be appropriately adjusted with the pH adjuster, the surfactant, and the like.

The inkjet ink of the present invention can be used in various fields, but it is suitable for water-based writing ink, water-based printing ink, information recording ink, textile printing, etc., and it is particularly preferable to use it as an ink for inkjet recording, which will be described later. It is preferably used in the inkjet recording method of the present invention.

The content of the coloring liquid contained in the inkjet ink is usually 2 to 35%, preferably 3 to 30%, and more preferably 5 to 30% by mass based on the total mass of the inkjet ink. . The content of the water-soluble organic solvent contained in the inkjet ink is usually 10 to 50%, preferably 15 to 50%, more preferably 20 to 50%, still more preferably 30 to 50%. The content of the ink modifiers is generally 0 to 25%, preferably 0.01 to 20%, based on the total weight of the inkjet ink.

From the point of view of high-speed ejection responsiveness, the above-mentioned inkjet ink preferably has a viscosity of about 3 to 20 mPa·s at 25° C. when measured with an E-type viscometer. Moreover, the surface tension is usually preferably in the range of 20 to 45 mN/m when measured by the plate method. In practice, it is preferable to adjust the physical properties to appropriate values in consideration of the ejection volume, response speed, ink droplet flight characteristics, etc. of the printer to be used.

(ink set)
An ink set of the inkjet ink described above and other inks is also included in the present invention. The ink set of the inkjet ink is preferably an ink set of the inkjet ink and an ink having a different color tone. For example, the inkjet ink and at least one selected from the group consisting of yellow ink, magenta ink, and cyan ink. An ink set containing one ink is preferred.

(hydrophobic fiber)
The present invention also includes a hydrophobic fiber printed using the inkjet ink or the ink set. Specific examples of the hydrophobic fibers include resins such as polyester, nylon, triacetate, diacetate and polyamide, and resins containing two or more of these resins. As the hydrophobic resin-containing fibers, fibers made of the above resins, and blended fibers of these fibers with regenerated fibers such as rayon and natural fibers such as cotton, silk, and wool are also hydrophobic in this specification. contained in fibers containing elastic resins. Some fibers are known to have an ink-receiving layer (anti-bleeding layer), and such fibers can also be used in the printing method described below. Fibers having an ink-receiving layer can be prepared by known methods or obtained commercially. The material, structure, and the like of the ink-receiving layer are not particularly limited, and can be appropriately used depending on the purpose. Specific examples of the fabric, which is a structure of fibers containing a hydrophobic resin, include satin, tropical, double picket, microfiber, and the like. Examples of films and sheets containing a hydrophobic resin include PET films and PET sheets; fabrics coated with hydrophobic resins, glass, metal, ceramics; and the like. The above "PET" is an abbreviation for "polyethylene terephthalate".

(Method for printing hydrophobic fiber)
The dyeing methods described above are methods for dyeing fibers or substances, and are roughly divided into two types.

The first method is a fiber dyeing method called direct printing or direct textile printing. This method includes a step A of attaching droplets of the inkjet ink to fibers containing a hydrophobic resin by an inkjet printer to form image information such as characters and patterns on the fibers, and the ink attached in the step A. A method for dyeing a fiber comprising at least three steps of a step B of fixing the dye in the droplets to the fiber by heat, and a step C of washing the unfixed dye remaining in the fiber. Step B is generally performed by known steaming or baking. For steaming, for example, a high temperature steamer is usually used at 170 to 180°C for approximately 10 minutes; and a high pressure steamer is usually used for approximately 20 minutes at 120 to 130°C; method. Baking (thermosol) includes, for example, a method of dyeing fibers by treating the fibers usually at 190° C. to 210° C. and usually about 60 seconds to 120 seconds. Step C is a step of washing the obtained fibers with warm water and, if necessary, water. Warm water or water used for washing may contain a surfactant. It is also preferable to dry the washed fibers usually at 50 to 120° C. for 5 to 30 minutes.

The textile printing method may further include a fiber pretreatment step for the purpose of preventing bleeding and the like. As the pretreatment step, there is a step of applying an aqueous solution containing at least one kind of sizing agent and optionally containing an alkaline substance, a reducing agent and a hydrotropic agent to the fibers before the ink is adhered. mentioned. In the step of applying the pretreatment, it is preferable to use an aqueous solution of a pretreatment agent containing at least a sizing agent as a pretreatment liquid, and apply the pretreatment liquid by coating or impregnating the fibers with the pretreatment liquid.

Examples of the sizing agent include natural gums such as guar and locust bean, starches, sodium alginate, seaweed such as funori, plant skins such as pectic acid, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and the like. cellulose derivatives, modified starches such as carboxymethyl starch, and synthetic glues such as polyvinyl alcohol and polyacrylic acid esters. Sodium alginate is preferred.

Examples of the alkaline substance include alkali metal salts of inorganic or organic acids; salts of alkaline earth metals; and compounds that liberate alkali when heated. Metal salts are preferred, including sodium compounds and potassium compounds. Specific examples include alkali metal hydroxides such as sodium hydroxide and calcium hydroxide; 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 formate and sodium trichloroacetate; and the like. Sodium hydrogen carbonate is preferred.

As the anti-reduction agent, sodium meta-nitrobenzenesulfonate is preferred. Examples of the hydrotropic agent include ureas such as urea and dimethylurea. Urea is preferred.

The paste, alkaline substance, anti-reduction agent, and hydrotropic agent may be a single compound or a combination of multiple compounds. The mixing ratio of each pretreatment agent in the total mass of the pretreatment liquid is, for example, 0.5 to 5% paste, 0.5 to 5% sodium bicarbonate, and 0 to 5% sodium metanitrobenzenesulfonate. , 1-20% urea and the balance water. The application of the pretreatment agent to fibers includes, for example, a padding method. The padding reduction rate is preferably about 40 to 90%, more preferably about 60 to 80%.

The second method is a method called sublimation transfer printing, sublimation transfer dyeing, or the like. In this method, droplets of the ink are deposited on an intermediate recording medium by an ink jet printer to obtain an intermediate recording medium on which image information such as characters and patterns are recorded. The dye in the ink droplets adhering to the intermediate recording medium is sublimated and transferred to the fibers by contacting and heating the adhering surface with a substance selected from fibers, films and sheets containing a hydrophobic resin. It is a method of dyeing a substance that is dyed by As the intermediate recording medium, it is preferable that the dye in the ink droplets adhering to the intermediate recording medium does not agglomerate on the surface thereof and does not interfere with the sublimation of the dye during sublimation transfer. An example of such an intermediate recording medium is paper having an ink-receiving layer formed on its surface with inorganic fine particles such as silica, and special paper for ink jet recording can be used. As a heating method for transferring the recorded image from the intermediate recording medium to the fiber, a method of dry heat treatment at about 190 to 200° C. is usually used.

The above intermediate recording medium is not particularly limited. Types of paper/paperboard and processed products (Nos. 6001 to 6284. However, No. 6235 “Oil resistance”, 6263 "Flute, corrugated", 6273 "Pulp molding", 6276 "Carbon paper", 6277 "Multi-copy form paper", 6278 "Back carbon foam paper"); varieties and processed products; and cellophane is referred to as "paper, etc."). Any of these papers can be used as the intermediate recording medium as long as it can be used for sublimation transfer. As described above, heat treatment at about 190.degree. C. to 210.degree. C. is usually performed when sublimation transfer is performed. Therefore, among the above intermediate recording media, those that are stable during heat treatment are preferred.

The above-mentioned inkjet ink can be used in various fields, but is suitable for water-based writing ink, water-based printing ink, information recording ink, textile printing, etc., and is particularly preferably used as an inkjet ink for textile printing.

According to the present invention, it is possible to expand the color reproduction range compared to conventional inkjet printing without using unlimited types and numbers of dyes as in the conventional printing method using colored glue or the like.
The colored liquid and the inkjet ink of the present invention do not cause aggregation or precipitation of solids even after long-term storage, and have good storage stability. In addition, changes in physical properties such as viscosity and average particle size are extremely small. In addition, the coloring liquid and inkjet ink of the present invention are not only excellent in color development, but also have various fastness properties such as light resistance, abrasion resistance, gas resistance, chlorine resistance, sweat resistance, and fastness to washing. Also excellent in sex.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In the examples, parts are by weight and % is by weight unless otherwise specified.

[Production Example 1 Preparation of Dispersant 1]
25 parts of Joncryl 678 (manufactured by BASF), 8.0 parts of 48% aqueous sodium hydroxide solution, 71.8 parts of deionized water, 0.1 part of Proxel GXL (manufactured by Arch Chemical Co.), Surfynol 104 (manufactured by Nissin Chemical Industry Co., Ltd.) was mixed, heated to 80-90° C. and stirred for 10 hours to obtain a 25% aqueous solution of Joncryl 678 (dispersant 1). .

[Production Example 2 Preparation of Dispersant 2]
25 parts of Joncryl 690 (manufactured by BASF), 9.0 parts of 48% aqueous sodium hydroxide solution, 71.8 parts of deionized water, 0.1 part of Proxel GXL (manufactured by Arch Chemical Co.), Surfynol 104 (manufactured by Nissin Chemical Industry Co., Ltd.) was mixed, heated to 80-90° C. and stirred for 10 hours to obtain a 25% aqueous solution of Joncryl 690 (dispersant 2). .

[Production Example 2-1 Preparation of 20% BPS-30]
20 parts of BPS-30 (manufactured by Nikko Chemicals Co., Ltd.) was added to 80 parts of deionized water, heated to 50-60° C. and stirred for 1 hour to obtain a solution “20% BPS-30”.

[Production Example 3 Preparation of Dispersion 1]
C. I. 15 parts of Disperse Blue 359, 18.8 parts of 40% Labelin W40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 3.8 parts of 20% BPS-30 obtained in Production Example 2-1, and ion-exchanged water. 71.8 parts, 0.1 part of Proxel GXL (manufactured by Arch Chemical Co., Ltd.), and 0.1 part of Surfynol 104 (manufactured by Nissin Chemical Industry Co., Ltd.) are mixed, glass beads are added, and a sand mill is used to Dispersion treatment was performed for 15 hours under water cooling. Next, the dispersion was filtered through glass fiber filter paper GC-50 (manufactured by Toyo Roshi Kaisha, Ltd., filter pore size 0.5 μm) to obtain a 15% aqueous dispersion (dispersion 1) from which components with large particle sizes were removed. Ta.

[Production Example 4 Preparation of Dispersion Liquid 2]
C. I. 15 parts of Disperse Blue 56 (manufactured by Jiangsu Yabang Dye Co., Ltd.), 18.8 parts of 40% Labelin W40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 20% BPS obtained in Production Example 2-1- 3.8 parts of 30, 71.8 parts of deionized water, 0.1 part of Proxel GXL (manufactured by Arch Chemical Co., Ltd.), and 0.1 part of Surfynol 104 (manufactured by Nissin Chemical Industry Co., Ltd.) are mixed. Then, glass beads were added, and dispersion treatment was performed for 15 hours under water cooling using a sand mill. Next, the dispersion was filtered through glass fiber filter paper GC-50 (manufactured by Toyo Roshi Kaisha, Ltd., filter pore size 0.5 μm) to obtain a 15% aqueous dispersion (dispersion 2) from which components with large particle sizes were removed. Ta.

[Examples 1 to 13] Preparation of Dispersions 1 to 13 Glass beads with a diameter of 0.2 mm were added to each component shown in Tables 1 and 2 below, and dispersion treatment was performed for 15 hours under water cooling in a sand mill. After dispersion treatment, an aqueous dispersion with a dye content of 15% was prepared. Next, the dispersion was filtered through glass fiber filter paper GC-50 (manufactured by Toyo Roshi Kaisha, Ltd., filter pore size 0.5 μm) to obtain an aqueous dispersion from which components with large particle sizes were removed. are defined as Dispersions 1 to 13, respectively.

[Comparative Examples 1 to 4] Preparation of Dispersion Liquids 14 to 17 Glass beads with a diameter of 0.2 mm were added to each component shown in Table 3 below, and dispersed in a sand mill under water cooling for about 15 hours. After dispersion treatment, an aqueous dispersion with a dye content of 15% was prepared. Next, the dispersion was filtered through glass fiber filter paper GC-50 (manufactured by Toyo Roshi Kaisha, Ltd., filter pore size 0.5 μm) to obtain an aqueous dispersion from which components with large particle sizes were removed. are defined as Dispersions 14 to 17, respectively. In addition, the dispersion liquid in the specification of the present application indicates the above colored liquid.

The abbreviations and the like in Tables 1 to 3 below represent the following.
DB359: C.I. I. Disperse Blue 359 (manufactured by Jiangsu Yabang Dye Co., Ltd.)
DB56: C.I. I. Disperse Blue 56 (manufactured by Jiangsu Yabang Dye Co., Ltd.)
DB81: C.I. I. Disperse Blue 81 (manufactured by Jiangsu Yabang Dye Co., Ltd.)
DB97: C.I. I. Disperse Blue 97 (manufactured by Jiangsu Yabang Dye Co., Ltd.)
DB145: C.I. I. Disperse Blue 145 (manufactured by Jiangsu Yabang Dye Co., Ltd.)
Vanilex N: lignin sulfonic acid (manufactured by Nippon Paper Industries Co., Ltd.)
Labelin W40: sodium naphthalenesulfonate formalin condensate (Daiichi Kogyo Seiyaku Co., Ltd.)
BPS-30: Nikkor BPS-30 (manufactured by Nikko Chemicals Co., Ltd.)
Surfynol 104: acetylene glycol surfactant (manufactured by Nissin Chemical Industry Co., Ltd.)
Proxel GXL (S): Proxel GXL (S) (manufactured by Arch Chemical Co.)

<Evaluation of dispersion liquid>
The dispersion liquids 1 to 15 obtained as described above were evaluated for the initial particle size of the dispersion liquid, the temporal particle size of the dispersion liquid, and the storage stability of the dispersion liquid by the evaluation methods described later. The initial particle size of the dispersion is synonymous with the number average particle size.

<Initial particle size of dispersion liquid>
Dispersions 1 to 15 of Examples and Comparative Examples in Tables 1 to 6 were each diluted 1000 times, and the volume average particle size (D10 D50 D90) was measured using Microtrac UPA (manufactured by Nikkiso Co., Ltd.). , D50 was taken as the initial particle size of the dispersion. Evaluation criteria are as follows. Rank 2 or less is a practically unbearable level.
(Evaluation criteria)
Rank 5: The initial particle size of the dispersion liquid is less than 100 nm.
Rank 4: The initial particle size of the dispersion liquid is 100 nm or more and less than 120 nm.
Rank 3: The initial particle size of the dispersion liquid is 120 nm or more and less than 150 nm.
Rank 2: The initial particle size of the dispersion liquid is 150 nm or more and less than 180 nm.
Rank 1: The initial particle size of the dispersion liquid is 180 nm or more.

<Dispersion particle size over time>
100 g of each of dispersion liquids 1 to 15 of Examples and Comparative Examples in Tables 1 to 6 was sealed in a glass bottle and allowed to stand at 60° C. for 14 days. After standing, the dispersion liquids 1 to 15 are each diluted 1000 times with water, and the volume average particle diameter (D50) is measured using Microtrac UPA (manufactured by Nikkiso Co., Ltd.), and the dispersion liquid particle diameter over time. and
Evaluation criteria are as follows. Rank 2 or less is a practically unbearable level.
(Evaluation criteria)
Rank 5: The initial particle size of the dispersion liquid is less than 100 nm.
Rank 4: The initial particle size of the dispersion liquid is 100 nm or more and less than 120 nm.
Rank 3: The initial particle size of the dispersion liquid is 120 nm or more and less than 150 nm.
Rank 2: The initial particle size of the dispersion liquid is 150 nm or more and less than 180 nm.
Rank 1: The initial particle size of the dispersion liquid is 180 nm or more.

<Dispersion Storage Stability>
Dispersions 1 to 15 of Examples and Comparative Examples in Tables 1 to 6 were each diluted 10,000 times, and the absorbance at the maximum absorption wavelength at 400 nm to 780 nm was measured. Next, 100 g of each of dispersions 1 to 42 were sealed in a glass bottle and allowed to stand at 60° C. for 14 days. After standing, each of the obtained dispersions 1 to 42 was diluted 10,000 times, and the absorbance at the maximum absorption wavelength was similarly measured. Taking the absorbance before standing as 100%, the absorbance after standing was calculated, and the value was used to evaluate the storage stability of the dispersion. Evaluation criteria are as follows. Rank 2 or less is a practically unbearable level.
(Evaluation criteria)
Rank 5: The absorbance after standing is 95% or more.
Rank 4: The absorbance after standing is 90% or more and less than 95%.
Rank 3: The absorbance after standing is 80% or more and less than 90%.
Rank 2: The absorbance after standing is 60% or more and less than 80%.
Rank 1: The absorbance after standing is less than 60%.

[Examples 12 to 22] Preparation of Inks 1 to 11 Inks 1 to 11 were obtained by mixing each component shown in Tables 4 and 5 below and stirring for 30 minutes. Each of the obtained inks was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC) to prepare test inks 1 to 11 each having a dye content of 5% for use in inkjet recording. Light fastness evaluation and results in Tables 4 and 5 will be described later.

[Comparative Examples 5 to 8] Preparation of Inks 12 to 15 Inks 12 to 15 were obtained by mixing each component shown in Table 6 below and stirring for 30 minutes. Each of the obtained inks was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC) to prepare test inks 12 to 15 each having a dye content of 5% for use in inkjet recording. The light fastness evaluation and results in Table 6 will be described later.

[Intermediate recording medium printed with ink and sublimation transfer textile printing using it]
Inks 1 to 15 of Examples and Comparative Examples listed in Tables 4 to 6 were filled in an inkjet printer (manufactured by EPSON Corporation, trade name PX-504A), and TRANSJET Eco II 8385 (95 g/ m ² ) to obtain an intermediate recording medium on which a 100% duty single-color solid image was printed. After superimposing the colored material adhering surface of each intermediate recording medium and a polyester cloth (Teijin Tropical), using a desktop automatic flat press machine (manufactured by Asahi Textile Machinery Co., Ltd.: AF-65TEN) 200 ° C. × 30 A dyed product dyed by the sublimation transfer dyeing method was obtained by heat-treating under the condition of 2 seconds. Each dyed product obtained was evaluated as follows.

[Light resistance test]
Using a low-temperature xenon weatherometer XL75 manufactured by Suga Test Instruments Co., Ltd., under the conditions of 100,000 Lux illumination, 60% RH humidity, and 24°C temperature, heat treatment was performed at 200°C for 30 seconds. , Each dyed article dyed by the sublimation transfer dyeing method was left for 24 hours. After the test, the degree of discoloration and fading of the portion irradiated with the xenon lamp on each dyed product was determined using a JIS blue scale for discoloration and fading. The higher the judgment grade, the lower the degree of discoloration and fading, which means excellent results. The test results are shown in Tables 4-6 above. Furthermore, colorimetry was performed on the dyed portion of each of the dyed products obtained in the above Examples and Comparative Examples. Specifically, the area of the dyed cloth irradiated with a xenon lamp and the area not irradiated are measured using a spectrophotometer "eXact (manufactured by X-rite)" to measure L*a*b*. did. Colorimetry was performed under the conditions of a D65 light source, a viewing angle of 2°, and status I. Tables 7 to 9 below show the results of calculating ΔEab for the locations irradiated with the xenon lamp and the locations not irradiated with the xenon lamp from the obtained results. The lower the value of ΔEab, the lower the degree of discoloration and fading.

From the results in Tables 4 to 9, it is clear that the colored liquids of the present invention and inks containing the same are excellent in light resistance.

The coloring liquid and inkjet ink of the present invention have good storage stability. In addition, changes in physical properties such as viscosity and average particle size are extremely small. In addition to being excellent in color development, it is also excellent in various fastness properties such as light resistance, abrasion resistance, gas resistance, chlorine resistance, sweat resistance, and fastness to washing.

Claims (15)

a compound represented by the following formula (1); I. A coloring liquid containing Disperse Blue 359.

(wherein X ₁ to X ₅ each independently represent a group selected from the group consisting of a hydrogen atom, an amino group and a hydroxy group; at least two of X ₁ to X ₄ are hydroxy groups; two are primary amino groups or hydrogen atoms. ) The compound represented by the above formula (1) is C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 81, C.I. I. Disperse Blue 97, C.I. I. 2. The coloring liquid according to claim 1, which is at least one selected from the group consisting of Disperse Blue 145. C.I. I. The content of Disperse Blue 359 and the content of the compound represented by the above formula (1) is the content weight ratio (C.I. Disperse Blue 359 and the compound represented by the above formula (1) ratio) is in the range of 1:0.3 to 1:4.0. The coloring liquid according to any one of claims 1 to 3, further comprising a dispersant. 5. The coloring liquid according to claim 4, wherein the dispersant is at least one dispersant selected from the group consisting of anionic dispersants, nonionic dispersants and polymeric dispersants. The anionic dispersant is at least one selected from the group consisting of formalin condensates of β-naphthalenesulfonates, formalin condensates of alkylnaphthalenesulfonates, and formalin condensates of creosote oil sulfonates. 5. The coloring liquid according to 5. 7. The coloring liquid according to claim 5 or 6, further comprising at least one selected from the group consisting of phytosterol compounds and cholestanol compounds. The coloring liquid according to any one of claims 5 to 7, wherein the polymeric dispersant comprises a styrene/acrylic polymer dispersant. The colored liquid according to any one of claims 1 to 8, further comprising an antifoaming agent. The coloring liquid according to any one of claims 1 to 9, further comprising a water-soluble organic solvent. The colored liquid according to any one of claims 1 to 10, further comprising a preservative. The colored liquid according to any one of claims 1 to 11, further comprising a rosin compound. The compound represented by the above formula (1) and the above C.I. I. 13. The colored liquid according to any one of claims 1 to 12, wherein Disperse Blue 359 forms particles having a number average particle diameter of 10 to 500 nm in the colored liquid. An inkjet ink comprising the coloring liquid according to any one of claims 1 to 13. An inkjet print printed using the inkjet ink of claim 14 .