Colored dispersion, colored dispersion set, recording media, and method for printing hydrophobic fibers.

Abstract

To provide: a color dispersion and a color dispersion set which are excellent in storage stability and odorlessness; a recording media having attached the color dispersion or each color dispersion which the color dispersion set comprises; and a printing method of hydrophobic fibers using the color dispersion or the color dispersion set.SOLUTION: Provided is a color dispersion, comprising a water-insoluble dye, a dispersant based on an aromatic sulfonic acid-formalin condensate, and water, where the dispersant based on an aromatic sulfonic acid-formalin condensate is a reaction product obtained from a condensation reaction of an aromatic sulfonic acid-based compound and formalin, comprising the compounds represented by the following formulas (1) to (3). When a total amount of the aromatic sulfonic acid-based compound is taken as 100 mass%, a total amount of the compounds represented by formulas (2) and (3) is more than 30 mass% and 95 mass% or less, and a total amount of the compound represented by formula (3) is more than 5 mass% and less than 70 mass%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a colored dispersion, a colored dispersion set comprising the colored dispersion, a recording medium to which the colored dispersion or each colored dispersion contained in the colored dispersion set is attached, and a method for printing hydrophobic fibers using the colored dispersion or the colored dispersion set. [Background technology]

[0002] In recent years, a recording method using inkjet-based, plateless printing has been proposed, and inkjet printing (inkjet textile printing) is now being used for textile printing, including cloth. Compared to conventional printing methods such as screen printing, inkjet printing offers various advantages, including being plateless, resource-saving, energy-saving, and facilitating high-definition reproduction.

[0003] Here, hydrophobic fibers, such as polyester fibers, are generally dyed with water-insoluble colorants. Therefore, for inkjet printing on hydrophobic fibers, it is generally necessary to use a dispersion ink with good dispersion stability and other properties, which is a water-based ink in which a water-insoluble colorant is dispersed in water.

[0004] Inkjet printing methods for hydrophobic fibers are broadly classified into direct printing and sublimation transfer. Direct printing is a printing method in which ink is directly applied (printed) to hydrophobic fibers, and then the dye in the ink is transferred to the hydrophobic fibers by heat treatment such as high-temperature steaming. On the other hand, sublimation transfer is a printing method in which ink is applied (printed) to an intermediate recording medium (such as a special transfer paper), the ink-applied surface of the intermediate recording medium is placed on top of the hydrophobic fibers, and then the dye is transferred from the intermediate recording medium to the hydrophobic fibers by heat.

[0005] Sublimation transfer is primarily used for printing banners and other similar items. The ink used contains easily sublimable dyes that are highly suitable for transfer to hydrophobic fibers through heat treatment. The processing involves two steps: (1) printing: applying dye ink to an intermediate recording medium using an inkjet printer, and (2) transfer: transferring and dyeing the dye from the intermediate recording medium into the fibers through heat treatment. Since commercially available transfer paper can be widely used, pre-treatment of the fibers is not required, and the washing step is also omitted.

[0006] For sublimation transfer inks, water-based inks, which are in which water-insoluble dyes are dispersed in water, are commonly used. Such inks are prepared, for example, by adding a water-soluble organic solvent as a humectant (anti-drying agent), a surfactant as a surface tension modifier, and other additives (pH adjusters, preservatives and antifungal agents, defoamers, etc.) to a colored dispersion liquid prepared by dispersing a sublimable dye selected from disperse dyes and oil-soluble dyes in water with a dispersant, and optimizing the physical properties (physical properties) such as particle size, viscosity, surface tension, and pH.

[0007] Dispersants known for dispersing disperse dyes include dispersants obtained by condensing sodium naphthalene sulfonate with formalin (see, for example, Patent Document 1) and dispersants obtained by condensing sodium β-naphthalene sulfonate with formalin (see, for example, Patent Document 2). However, there are many types of disperse dyes, each with a different chemical structure, and the hydrophilic-hydrophobic balance also differs depending on the type of disperse dye. For this reason, when using dispersants obtained by condensing a single component such as sodium naphthalene sulfonate or sodium β-naphthalene sulfonate with formalin, the adsorption to the disperse dye is weak, and the dispersion stability of the colored dispersion or ink is not satisfactory.

[0008] Furthermore, a dispersant obtained by condensing sodium creosote oil sulfonate with formalin (see, for example, Patent Document 3) is also known as a dispersant for dispersing disperse dyes and the like. Because such a dispersant uses creosote oil containing multiple aromatic compounds as a raw material, it exhibits strong adsorption to various disperse dyes, and the dispersion stability of the colored dispersion or ink can be satisfied to a certain extent. On the other hand, it was not satisfactory in terms of odor. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 9-291235 [Patent Document 2] Japanese Patent Publication No. 2003-246954 [Patent Document 3] International Publication No. 2005 / 121263 [Overview of the project] [Problems that the invention aims to solve]

[0010] The present invention aims to provide a colored dispersion with excellent storage stability and low odor, a colored dispersion set comprising the colored dispersion, a recording medium to which the colored dispersion or the colored dispersion set is attached, and a method for printing hydrophobic fibers using the colored dispersion or the colored dispersion set. [Means for solving the problem]

[0011] The following embodiments are specific means for solving the above problems. 1) It contains a water-insoluble dye, an aromatic sulfonic acid formalin condensate-based dispersant, and water. The aforementioned aromatic sulfonic acid formalin condensate dispersant is a reaction product obtained by a condensation reaction between an aromatic sulfonic acid compound and formalin. The aforementioned aromatic sulfonic acid compound includes a compound represented by the following formulas (1) to (3): When the total amount of the aromatic sulfonic acid compound is 100% by mass, the total amount of the compound represented by the following formula (2) and the compound represented by the following formula (3) exceeds 30% by mass and is 95% by mass or less, and the total amount of the compound represented by the following formula (3) exceeds 5% by mass and is less than 70% by mass, a colored dispersion.

[0012]

Chemical formula

[0013] 2) When the total amount of the aromatic sulfonic acid compound is 100% by mass, the total amount of the compound represented by the formula (2) and the compound represented by the formula (3) is 40 to 95% by mass, and the total amount of the compound represented by the formula (3) is 10 to 60% by mass, the colored dispersion according to 1).

[0014] 3) The aromatic sulfonic acid compound further contains a compound represented by the following formula (4), the colored dispersion according to 1) or 2).

[0015]

Chemical formula

[0016] 4) Furthermore, it contains at least one selected from the group consisting of an alkylene oxide adduct of phytosterol, an alkylene oxide adduct of hydrogenated phytosterol, an alkylene oxide adduct of cholestanol, and an alkylene oxide adduct of hydrogenated cholestanol, the colored dispersion according to any one of 1) to 3).

[0017] 5) Furthermore, a colored dispersion according to any one of items 1) to 4), which contains a polysiloxane compound.

[0018] 6) Furthermore, a colored dispersion according to any one of items 1) to 5), which contains glycol ether.

[0019] 7) A colored dispersion according to any one of items 1) to 6), wherein the average particle size of the water-insoluble dye is 60 to 200 nm.

[0020] 8) A colored dispersion set comprising a colored dispersion described in any one of items 1) to 7), and at least one other colored dispersion having a different hue from the colored dispersion.

[0021] 9) A colored dispersion as described in any one of items 1) to 7), or a recording medium to which each colored dispersion provided in the colored dispersion set described in item 8) is attached.

[0022] 10) The recording medium according to 9), wherein the recording medium is a hydrophobic fiber.

[0023] 11) A printing step to obtain a recorded image by attaching droplets of each colored dispersion from any one of items 1) to 7) or the colored dispersion set described in 8) to an intermediate recording medium, A transfer step in which hydrophobic fibers are brought into contact with the surface on which the droplets are attached in the intermediate recording medium and heat-treated to transfer the recorded image to the hydrophobic fibers, A method for printing hydrophobic fibers containing [a specific substance]. [Effects of the Invention]

[0024] According to the present invention, it is possible to provide a colored dispersion with excellent storage stability and low odor, a colored dispersion set comprising the colored dispersion, a recording medium to which the colored dispersion or each colored dispersion contained in the colored dispersion set is attached, and a method for printing hydrophobic fibers using the colored dispersion or the colored dispersion set. [Modes for carrying out the invention]

[0025] The following describes in detail specific embodiments to which the present invention is applied. In this specification, "CI" is an abbreviation for Color Index.

[0026] <Colored dispersion> The colored dispersion according to this embodiment contains a water-insoluble dye, an aromatic sulfonic acid formalin condensate-based dispersant, and water. The aromatic sulfonic acid formalin condensate-based dispersant is a reaction product obtained by a condensation reaction between an aromatic sulfonic acid compound and formalin. The aromatic sulfonic acid compound includes compounds represented by the following formulas (1) to (3). When the total amount of the aromatic sulfonic acid compound is 100% by mass, the total amount of the compound represented by the following formula (2) and the compound represented by the following formula (3) is greater than 30% by mass and less than 95% by mass, and the total amount of the compound represented by the following formula (3) is greater than 5% by mass and less than 70% by mass.

[0027] [ka] (In the formula, M 1 M 2 M 3 Each of these independently represents a hydrogen atom, a metal ion, or an ammonium ion.

[0028] The components contained in the colored dispersion according to this embodiment will be described in detail below. Each of the components described below may be used individually or in combination of two or more.

[0029] [Water-insoluble dyes] Water-insoluble dyes refer to dyes whose solubility in water at 25°C is typically 3 g / L or less, preferably 2 g / L or less, and more preferably 1 g / L or less.

[0030] Examples of water-insoluble dyes include disperse dyes and oil-soluble dyes, and it is preferable to use disperse dyes.

[0031] Specific examples of water-insoluble dyes include, for example, CI Disperse Yellow 3, 4, 5, 7, 8, 9, 13, 23, 24, 30, 33, 34, 39, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 114, 116, 118, 119 , 122, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 186, 192, 198, 199, 200, 202, 204, 210, 211, 215, 216, 218, 224, 232, 237; CI Disperse Orange 1, 1:1, 3, 5, 7, 11, 13, 17, 20, 21, 23, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 47, 48, 49, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 86, 89, 90, 91, 93, 96, 97, 118, 119, 127, 130, 139, 142; CI Disperse Thread 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 55:1, 56, 58, 59, 60, 65, 70, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 1 53, 154, 157, 158, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 2 CIDisperse Violet: 1, 4, 8, 11, 17, 23, 26, 27, 28, 29, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, 77, 97; CI Disperse Green: 9; CI Disperse Brown: 1, 2, 4, 9, 13, 19; CI Disperse Blue 3, 5, 7, 9, 14, 16, 19, 20, 26, 26:1, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 64:1, 71, 72, 72:1, 73, 75, 77, 79, 79:1, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 131, 139, 141, 142, 143, 145, 146, 148, 149, 153, 154, 158, 165, 1 65:1, 165:2, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 266, 267, 270, 281, 284, 285, 287, 288, 291, 293, 295, 297, 301, 315, 330, 333, 341, 353, 354, 358, 359, 360, 364, 365, 366, 368; CI Disperse Black Examples include 1, 3, 10, 24; CI Solvent Yellow 114; CI Solvent Orange 60, 67; CI Solvent Red 146; CI Solvent Blue 36, 63, 83, 105, 111; etc. Among these, CI Disperse Yellow 54; CI Disperse Orange 25; CI Disperse Red 60; CI Disperse Blue 359, 360; and CI Solvent Orange 60; are preferred.

[0032] As a water-insoluble dye, it is also preferable to use a combination of a dye derivative described in International Publication No. 2020 / 204041 (hereinafter also referred to as "dye derivative X1") and a water-insoluble dye (hereinafter also referred to as "water-insoluble dye Y1").

[0033] As the water-insoluble dye Y1, for example, CI Disperse Thread 60 is preferred.

[0034] As the dye derivative X1, for example, CI Disperse Red 92, 146; anthraquinone compounds E, F, H, I described in International Publication No. 2020 / 204041; are preferred, with CI Disperse Red 92 being more preferred.

[0035] Among the combinations of water-insoluble dye Y1 and dye derivative X1, the combination of CI Disperse Thread 60 and at least one dye derivative selected from the group consisting of CI Disperse Thread 92, 146; and anthraquinone compounds E, F, H, I; is preferred, and the combination of CI Disperse Thread 60 and CI Disperse Thread 92 is more preferred.

[0036] The mixing ratio of water-insoluble dye Y1 and dye derivative X1 can be set arbitrarily. The ratio (Y1 / X1) of the mass of water-insoluble dye Y1 to the mass of dye derivative X1 (X1) preferably satisfies the relationship 400 > (Y1 / X1) > 3.125, and more preferably satisfies the relationship 400 > (Y1 / X1) > 19.

[0037] Furthermore, it is also preferable to use a combination of CI Disperse Orange 25 (hereinafter also referred to as "DOr25") as a water-insoluble dye and at least one dye selected from the dyes represented by formula (1) and formula (2) described in International Publication No. 2020 / 235560 (hereinafter also referred to as "combined dye X2").

[0038] For example, the blended dye X2 is preferably CI Disperse Orange 49, 62, 71, 73, or 148, and more preferably CI Disperse Orange 73.

[0039] The mixing ratio of DOr25 and blended dye X2 can be set arbitrarily. When the total content of DOr25 and blended dye X2 is 100 parts by mass, the content of blended dye X2 is preferably less than 10 parts by mass, and more preferably 0.5 to 5 parts by mass.

[0040] Water-insoluble dyes may be in the form of powdered or lumpy dry dyes, or they may be wet cakes or slurries. They may also contain small amounts of dispersants such as surfactants to suppress the aggregation of dye particles during or after dye synthesis. Commercially available dyes come in various grades, including those for industrial dyeing, resin coloring, inks, toners, and inkjet applications, each differing in manufacturing method, purity, and dye particle size. To suppress aggregation after grinding, dyes with smaller particle sizes are preferable, and those with as few impurities as possible are preferable due to their impact on dispersion stability and discharge accuracy.

[0041] To adjust the color tone, it is possible to blend two or more water-insoluble dyes. For example, a black color can be created by mixing a blue dye with orange and red dyes as appropriate, and this can then be used as a black dye. Alternatively, two or more water-insoluble dyes may be blended to fine-tune the color tone of blue, orange, red, violet, black, etc., to a desired level.

[0042] In the colored dispersion according to this embodiment, if a water-insoluble dye is contained in particulate form, the average particle size is preferably 60 to 200 nm. The average particle size is the particle size calculated using D50 (50% cumulative volume particle diameter) and is measured by the dynamic light scattering method or laser diffraction method described in JIS Z8825. Specifically, it can be measured using a particle size analyzer that uses the dynamic light scattering method as its measurement principle, such as Microtrac UPA, Nanotrac Wave-UT151, Nanotrac Wave-EX150 (all manufactured by Microtrac-Bell Co., Ltd.); ELSZ-2, DLS-8000 (both manufactured by Otsuka Electronics Co., Ltd.); LB-550 (manufactured by Horiba, Ltd.).

[0043] The content rate of the water-insoluble dye is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, based on the total amount of the colored dispersion liquid.

[0044] [Aromatic sulfonic acid formalin condensate-based dispersant] The aromatic sulfonic acid formalin condensate-based dispersant is a reaction product obtained by a condensation reaction of an aromatic sulfonic acid-based compound and formalin.

[0045] The aromatic sulfonic acid-based compound used in the condensation reaction includes compounds represented by the following formulas (1) to (3).

[0046] [Chemical formula] (In the formula, M 1 , M<000000�>, M 3 each independently represents a hydrogen atom, a metal ion, or an ammonium ion.)

[0047] M 1 ~M 3 Examples of the metal ion represented by M

[0048] M 1 ~M 3 include sodium ion, potassium ion, calcium ion, magnesium ion, etc., and sodium ion is preferred. Examples of the ammonium ion represented by M

[0049] include ammonium ion, methylammonium ion, dimethylammonium ion, trimethylammonium ion, tetramethylammonium ion, tetra-n-butylammonium ion, etc.

[0050] Examples of compounds represented by the above formula (2) include sodium salts of sulfonates of methylnaphthalene (1-methylnaphthalene, 2-methylnaphthalene, etc.).

[0051] Examples of compounds represented by formula (3) above include sodium salts of sulfonates of dimethylnaphthalene (1,5-dimethylnaphthalene, 1,4-dimethylnaphthalene, 2,7-dimethylnaphthalene, 2,3-dimethylnaphthalene, 1,3-dimethylnaphthalene, etc.).

[0052] When the total amount of aromatic sulfonic acid compounds used in the condensation reaction is taken as 100% by mass, the total amount of the compound represented by formula (2) and the compound represented by formula (3) is greater than 30% by mass and less than or equal to 95% by mass, preferably between 40% and 95% by mass. Furthermore, when the total amount of aromatic sulfonic acid compounds is taken as 100% by mass, the total amount of the compound represented by formula (3) is greater than 5% by mass and less than 70% by mass, preferably between 10% and 60% by mass. The total amount of the compound represented by formula (1) is greater than 0% by mass.

[0053] The aromatic sulfonic acid compound used in the condensation reaction may further include a compound represented by the following formula (4).

[0054] [ka] (In the formula, M 4 (This represents a hydrogen atom, a metal ion, or an ammonium ion.)

[0055] M 4 The metal ions and ammonium ions shown are M 1 ~M 3 It may be the same as that.

[0056] When the aromatic sulfonic acid compound used in the condensation reaction includes the compound represented by formula (4) above, the total amount of the compound represented by formulas (2) to (4) above relative to the total amount of the aromatic sulfonic acid compound is preferably more than 35% by mass and 95% by mass or less, more preferably 40 to 95% by mass, and even more preferably more than 40% by mass and 95% by mass or less. Furthermore, the total amount of the compound represented by formula (4) above relative to the total amount of the aromatic sulfonic acid compound is preferably 1 to 20% by mass, more preferably 2 to 10% by mass, and even more preferably 3 to 7% by mass.

[0057] Aromatic sulfonic acid formalin condensate dispersants can be produced, for example, by methods described in Japanese Patent Publication No. 2009-079010, Japanese Patent Publication No. 2007-099983, Japanese Patent Publication No. 2007-099719, Japanese Patent Publication No. 2016-124932, etc. Specifically, they can be obtained by heating naphthalene, methylnaphthalene, dimethylnaphthalene, etc. in sulfuric acid to perform sulfonation, and then carrying out a condensation reaction with formalin.

[0058] The content of the aromatic sulfonic acid formalin condensate-based dispersant is preferably 0.01 to 50% by mass, and more preferably 0.1 to 30% by mass, relative to the total amount of the colored dispersion.

[0059] [water] The water used is preferably deionized water, distilled water, or ultrapure water, which contains few impurities. Sterilized water may also be used.

[0060] The water content is preferably 10 to 99.5% by mass, and more preferably 20 to 90% by mass, relative to the total amount of the colored dispersion.

[0061] [Phytosterol alkylene oxide adducts, etc.] The colored dispersion according to this embodiment preferably further contains at least one selected from the group consisting of alkylene oxide adducts of phytosterols, alkylene oxide adducts of hydrogenated phytosterols, alkylene oxide adducts of cholestanol, and alkylene oxide adducts of hydrogenated cholestanol. Hereinafter, phytosterols and hydrogenated phytosterols will be collectively referred to as "phytosterols." Similarly, cholestanols and hydrogenated cholestanols will be collectively referred to as "cholestanols."

[0062] As alkylene oxide adducts of phytosterols, for example, C2-C4 alkylene oxide adducts of phytosterols are preferred, and ethylene oxide adducts are more preferred. Similarly, as alkylene oxide adducts of cholestanols, for example, C2-C4 alkylene oxide adducts of cholestanols are preferred, and ethylene oxide adducts are more preferred.

[0063] The amount of alkylene oxide (preferably C2-C4 alkylene oxide, more preferably ethylene oxide) added per equivalent of phytosterols or cholestanols is preferably about 10 to 50 equivalents, and the HLB is preferably about 13 to 20.

[0064] Examples of commercially available ethylene oxide adducts of phytosterols include NIKKOL BPS-20, NIKKOL BPS-30 (both manufactured by Nikko Chemicals Co., Ltd., ethylene oxide adducts of phytosterols), and NIKKOL BPSH-25 (same, ethylene oxide adduct of hydrogenated phytosterol). Examples of commercially available alkylene oxide adducts of cholestanols include NIKKOL DHC-30 (same, ethylene oxide adduct of cholestanol).

[0065] If the colored dispersion according to this embodiment contains phytosterol alkylene oxide adducts or the like, the content thereof is preferably 0.001 to 5% by mass, and more preferably 0.01 to 3% by mass, relative to the total amount of the colored dispersion.

[0066] [Polysiloxane compounds] The colored dispersion according to this embodiment preferably further contains a polysiloxane compound in order to improve the ejection response in an inkjet printer and to adjust the surface tension. Examples of polysiloxane compounds include polyether-modified siloxane and polyether-modified polydimethylsiloxane. Commercially available products include BYK-347 (manufactured by Bic Chemie, polyether-modified siloxane) and BYK-348 (same, polyether-modified polydimethylsiloxane).

[0067] If the colored dispersion according to this embodiment contains a polysiloxane compound, its content is preferably 0.01 to 3% by mass, and more preferably 0.01 to 1.5% by mass, relative to the total amount of the colored dispersion.

[0068] [Glycol ether] The colored dispersion according to this embodiment preferably further contains a glycol ether. Examples of glycol ethers include monoalkyl ethers of glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol, and methoxy glycol. Among these, methyl triglycol (triethylene glycol monomethyl ether), butyl triglycol (triethylene glycol monobutyl ether), butyl diglycol (diethylene glycol monobutyl ether), dipropylene glycol monopropyl ether, and methoxy glycol are preferred, with methoxy glycol being more preferred.

[0069] If the colored dispersion according to this embodiment contains glycol ether, its content is preferably 0.01 to 90% by mass, and more preferably 0.01 to 85% by mass, relative to the total amount of the colored dispersion.

[0070] [Additives] The colored dispersion according to this embodiment may contain additives other than those mentioned above. Examples of additives include dispersants (excluding the aromatic sulfonic acid formalin condensate-based dispersants mentioned above), water-soluble organic solvents (excluding the glycol ethers mentioned above), preservatives, surfactants, pH adjusters, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, viscosity modifiers, dye dissolving agents, antioxidants, resin emulsions, and the like.

[0071] Examples of dispersants other than the aromatic sulfonic acid formalin condensate-based dispersants mentioned above include styrene-(meth)acrylic copolymers, formalin condensates of aromatic sulfonic acids or their salts, polyoxyethylene arylphenyl ethers, polyoxyethylene arylphenyl ether sulfates, and polyoxyethylene naphthyl ethers.

[0072] Styrene-(meth)acrylic copolymers are copolymers of styrene monomers and (meth)acrylic monomers. Specific examples of copolymers include (α-methyl)styrene-acrylic acid copolymer, (α-methyl)styrene-acrylic acid-acrylic acid ester copolymer, (α-methyl)styrene-methacrylic acid copolymer, (α-methyl)styrene-methacrylic acid-acrylic acid ester copolymer, (α-methyl)styrene-acrylic acid ester-(anhydride) maleic acid copolymer, acrylic acid ester-styrene sulfonic acid copolymer, and (α-methyl)styrene-methacrylic sulfonic acid copolymer. In this specification, "(meth)acrylic" is used to include "acrylic" and "methacrylic". Similarly, "(α-methyl)styrene" is used to include "α-methylstyrene" and "styrene".

[0073] The mass-average molecular weight of the styrene-(meth)acrylic copolymer is preferably 1,000 to 20,000, more preferably 2,000 to 19,000, and even more preferably 5,000 to 17,000. The mass-average molecular weight of the styrene-(meth)acrylic copolymer can be measured by GPC (gel permulation chromatography).

[0074] The acid value of the styrene-(meth)acrylic copolymer is preferably, for example, 50 to 250 mg KOH / g, more preferably 100 to 250 mg KOH / g, and even more preferably 150 to 250 mg KOH / g. Setting the acid value to 50 mg KOH / g or higher tends to improve solubility in water and also improve dispersion stabilization for water-insoluble dyes. Setting the acid value to 250 mg KOH / g or lower tends to suppress blurring of printed images due to increased affinity with aqueous media. The acid value of the resin represents the number of mg of KOH required to neutralize 1 g of resin and can be measured according to JIS-K3054.

[0075] The glass transition temperature of the styrene-(meth)acrylic copolymer is preferably, for example, 45 to 135°C, more preferably 55 to 120°C, and even more preferably 60 to 110°C.

[0076] Examples of commercially available styrene-(meth)acrylic copolymers include Joncryl 67, 678, 680, 682, 683, 690, 52J, 57J, 60J, 63J, 70J, JDX-6180, HPD-196, HPD96J, PDX-6137A, 6610, JDX-6500, JDX-6639, PDX-6102B, and PDX-6124 (all manufactured by BASF). Among these, Joncryl 67 (weight-average molecular weight: 12500, acid value: 213 mgKOH / g), 678 (weight-average molecular weight: 8500, acid value: 215 mgKOH / g), 682 (weight-average molecular weight: 1700, acid value: 230 mgKOH / g), 683 (weight-average molecular weight: 4900, acid value: 215 mgKOH / g), and 690 (weight-average molecular weight: 16500, acid value: 240 mgKOH / g) are preferred, with Joncryl 678 being more preferred.

[0077] Examples of formalin condensates of aromatic sulfonic acids or their salts include creosote oil sulfonic acid, cresol sulfonic acid, phenol sulfonic acid, β-naphthalene sulfonic acid, β-naphthol sulfonic acid, β-naphthalene sulfonic acid, benzene sulfonic acid, cresol sulfonic acid, 2-naphthol-6-sulfonic acid, lignin sulfonic acid, and their respective formalin condensates or salts (sodium salts, potassium salts, lithium salts, etc.). Among these, formalin condensates of creosote oil sulfonic acid, β-naphthalene sulfonic acid, lignin sulfonic acid, and methylnaphthalene sulfonic acid or their salts are preferred.

[0078] Formalin condensates of aromatic sulfonic acids are available commercially. For example, examples of formalin condensates of β-naphthalene sulfonic acid include Demol N (manufactured by Kao Corporation) and the Avolan IS series (manufactured by Tanatex Chemicals Japan Co., Ltd.). Examples of formalin condensates of creosote oil sulfonic acid include Demol C (manufactured by Kao Corporation) and the Labelin W series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Examples of formalin condensates of special aromatic sulfonic acids include Demol SN-B (manufactured by Kao Corporation). Examples of formalin condensates of methylnaphthalene sulfonic acid include the Labelin AN series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Among these, Demol N, the Labelin AN series, and the Labelin W series are preferred, Demol N and the Labelin W series are more preferred, and the Labelin W series is even more preferred. Examples of lignin sulfonic acid include Vanillex N, Vanillex RN, Vanillex G, and Pearllex DP (all manufactured by Nippon Paper Industries Co., Ltd.).

[0079] Examples of polyoxyethylene arylphenyl ethers include styrylphenol compounds such as polyoxyethylene monostyrylphenyl ether, polyoxyethylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, and polyoxyethylene tetrastyrylphenyl ether; benzylphenol compounds such as polyoxyethylene monobenzylphenyl ether, polyoxyethylene dibenzylphenyl ether, and polyoxyethylene tripenzylphenyl ether; cumylphenol compounds such as polyoxyethylene cumylphenyl ether; polyoxyethylene naphthylphenyl ether, polyoxyethylene biphenyl ether, and polyoxyethylene phenoxyphenyl ether. Among these, polyoxyethylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, polyoxyethylene dibenzylphenyl ether, polyoxyethylene tripenzylphenyl ether, and polyoxyethylene cumylphenyl ether are preferred.

[0080] The number of repeating polyoxyethylene groups in polyoxyethylene arylphenyl ether is preferably 1 to 30, and more preferably 15 to 30. When the number of repeating groups is 1 or more, the compatibility with aqueous solvents tends to be excellent. Also, when the number of repeating groups is 30 or less, the viscosity tends not to become too high.

[0081] Examples of commercially available polyoxyethylene arylphenyl ethers include the Neugen EA series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); Paionin D-6112, Paionin D-6115, Paionin D-6120, Paionin D-6131, Paionin D-6512, Takesurf D-6413, DTD-51, Paionin D-6112, Paionin D-6320 (all manufactured by Takemoto Oil & Fat Co., Ltd.); TS-1500, TS-2000, TS-2600, SM-174N (all manufactured by Toho Chemical Co., Ltd.); Emulgen A60, Emulgen A90, Emulgen A500 (all manufactured by Kao Corporation); Emulgen B-66, Newcol CMP series (all manufactured by Nippon Emulsifier Co., Ltd.).

[0082] Examples of polyoxyethylene arylphenyl ether sulfates include the sulfates of the polyoxyethylene arylphenyl ethers mentioned above.

[0083] Examples of commercially available polyoxyethylene arylphenyl ether sulfates include SM-57, SM-130, and SM-210 (all manufactured by Toho Chemical Co., Ltd.).

[0084] Examples of commercially available polyoxyethylene naphthyl ethers include the Neugen EN series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and Paionin D-7240 (manufactured by Takemoto Oil & Fat Co., Ltd.).

[0085] If the colored dispersion according to this embodiment contains a dispersant other than the aromatic sulfonic acid formalin condensate-based dispersant described above, the content of the dispersant is preferably 50 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the aromatic sulfonic acid formalin condensate-based dispersant.

[0086] Examples of water-soluble organic solvents other than glycol ethers include polyhydric alcohols and pyrrolidones. Examples of polyhydric alcohols include C2-C6 polyhydric alcohols having 2 to 3 alcoholic hydroxyl groups. Examples of pyrrolidones include 2-pyrrolidone and N-methyl-2-pyrrolidone. For convenience, compounds that dissolve in water and act as wetting agents are also included in water-soluble organic solvents. Examples of such compounds include urea, ethylene urea, and sugars.

[0087] Examples of preservatives include compounds such as organic sulfur, organic nitrogen sulfur, organic halogen, haloallyl sulfone, iodopropagyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzothiazole, isothiazolin, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone, benzyl bromacetate, and inorganic salts. Specific examples of organic halogen compounds include sodium pentachlorophenol. Specific examples of pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide. Specific examples of isothiazolin compounds include 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, and 2-methyl-4-isothiazolin-3-one calcium chloride. Other specific examples of preservatives and fungicides include anhydrous sodium acetate, sodium sorbate, sodium benzoate, and Lonza brand names such as Proxel GXL and Proxel XL-2.

[0088] Examples of known surfactants include anionic, cationic, amphoteric, nonionic, and fluorinated surfactants.

[0089] Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and their salts, N-acyl methyl taurates, alkyl sulfates, polyoxyalkyl ether sulfates, alkyl sulfates, polyoxyethylene alkyl ether phosphates, rosinic acid soaps, castor oil sulfates, lauryl alcohol sulfates, alkylphenol type phosphates, alkyl type phosphates, alkylaryl sulfonates, diethyl sulfosaturates, diethylhexyl sulfosaturates, and dioctyl sulfosaturates. Examples of commercially available products include Hi-Tenol LA-10, LA-12, LA-16, Neo-Hi-Tenol ECL-30S, and ECL-45, all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0090] Examples of cationic surfactants include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

[0091] Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, polyoctyl polyaminoethylglycine, and imidazoline derivatives.

[0092] Nonionic surfactants include, for example, ether-based surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether; ester-based surfactants such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, and polyoxyethylene stearate; acetylene glycol (alcohol)-based surfactants such as 2,4,7,9-tetramethyl-5-decine-4,7-diol, 3,6-dimethyl-4-octin-3,6-diol, and 3,5-dimethyl-1-hexyn-3-ol; Surfinol 104, 105, 82, 465, and Olfin STG manufactured by Air Products Japan Co., Ltd.; and polyglycol ether-based surfactants (for example, Tergitol manufactured by SIGMA-ALDRICH). Examples include 15-S-7, etc.

[0093] Examples of fluorinated surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains. Examples of commercially available products include Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30, FS-31 (all manufactured by DuPont); PF-151N, PF-154N (both manufactured by Omnova); and others.

[0094] Any substance can be used as a pH adjuster, as long as it can control the pH of the prepared colored dispersion to approximately 5-11 without adversely affecting the colored dispersion. Specific examples 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 bicarbonate, and potassium carbonate; alkali metal salts of organic acids such as potassium acetate; and inorganic bases such as sodium silicate and disodium phosphate. Among these, triethanolamine is preferred.

[0095] Examples of chelating reagents include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracildiacetate.

[0096] Examples of rust inhibitors include acidic sulfites, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitride, pentaerythritol tetranitrate, and dicyclohexylammonium nitride.

[0097] Examples of water-soluble ultraviolet absorbers include sulfonated benzophenone compounds, benzotriazol compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

[0098] Examples of water-soluble polymer compounds include polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

[0099] Viscosity modifiers include water-soluble organic solvents as well as water-soluble polymer compounds, such as polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

[0100] Examples of dye dissolving agents include urea, ε-caprolactam, and ethylene carbonate.

[0101] Various organic and metal complex-based colorfastness inhibitors can be used as antioxidants. Examples of organic colorfastness inhibitors include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocyclic compounds. Examples of metal complex-based colorfastness inhibitors include nickel complexes and zinc complexes.

[0102] Examples of resin emulsions include emulsions formed from acrylic resins, epoxy resins, urethane resins, polyether resins, polyamide resins, unsaturated polyester resins, phenolic resins, silicone resins, fluororesins, polyvinyl resins (vinyl chloride, vinyl acetate, polyvinyl alcohol, etc.), alkyd resins, polyester resins, amino materials (melamine resins, urea resins, urea resins, melamine-formaldehyde resins, etc.). The resin emulsion may contain two or more resins. Furthermore, two or more resins may form a core / shell structure. Among resin emulsions, urethane resin emulsions are preferred.

[0103] Urethane resin emulsions are available commercially, and most are emulsions with a solid content concentration of 30-60% by mass. Examples of commercially available urethane resin emulsions include Permarin UA-150, 200, 310, 368, 3945, and U-Coat UX-320 (all manufactured by Sanyo Chemical Industries, Ltd.); Hydran WLS-201, 210, and HW-312B latex (all manufactured by DIC Corporation); and Superflex 150, 170, and 470 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Among these, examples of polycarbonate-based urethane resins include Permarin UA-310, 3945, and U-Coat UX-320. Examples of polyether-based urethane resins include Permarin UA-150, 200, and U-Coat UX-340.

[0104] The urethane resin in the urethane resin emulsion has an SP value of 8-24 (cal / cm³). 3 ) 1 / 2 Preferably, it is 8-17 (cal / cm³). 3 ) 1 / 2 It is more preferable that it be 8-11 (cal / cm 3 ) 1 / 2 It is even more preferable that this is the case. The SP value of the urethane resin is calculated by the Fedors method. If the urethane resin has acidic groups and these acidic groups are neutralized to prepare the emulsion, the SP value of the urethane resin before neutralization is used.

[0105] If the urethane resin in the urethane resin emulsion has acidic groups such as carboxyl groups, sulfo groups, or hydroxyl groups, these acidic groups may be alkali-chlorinated. For example, the acidic groups can be alkali-chlorinated by adding the urethane resin having acidic groups to water, stirring to prepare an aqueous solution, and then adding an alkaline compound to adjust the pH to 6.0 to 12.0. Examples of alkaline compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; and alkaline earth metal hydroxides such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide. One alkaline compound may be used alone, or two or more may be used in combination.

[0106] [Method for preparing colored dispersions, etc.] A method for preparing the colored dispersion according to this embodiment includes, for example, preparing an aqueous dispersion containing a water-insoluble dye and an aromatic sulfonic acid formalin condensate-based dispersant, and adding other components as needed.

[0107] Known methods for preparing aqueous dispersions include stirring and mixing the components constituting the aqueous dispersion using a sand mill (bead mill), roll mill, ball mill, paint shaker, ultrasonic disperser, high-pressure emulsifier, etc. For example, when using a sand mill, first, each component and beads as the dispersion medium are loaded into the sand mill. Glass beads, zirconia beads, etc., with a particle size of 0.01 to 1 mm can be used as beads. The amount of beads used is preferably 2 to 6 parts by mass per 1 part by mass of the material to be dispersed. Next, the sand mill is operated to perform the dispersion treatment. The dispersion treatment conditions are preferably 1000 to 2000 rpm for 1 to 20 hours. After the dispersion treatment, the beads are removed by filtration or the like to obtain an aqueous dispersion.

[0108] The prepared colored dispersion may be subjected to microfiltration using a membrane filter or the like. In particular, when the colored dispersion is used as an inkjet printing ink, it is preferable to perform microfiltration to prevent nozzle clogging and the like. The pore size of the filter used for microfiltration is usually 0.1 to 1 μm, and preferably 0.1 to 0.8 μm.

[0109] The viscosity of the colored dispersion according to this embodiment at 25°C is preferably about 3 to 20 mPa·s when measured with an E-type viscometer, from the viewpoint of high-speed ejection response. Furthermore, the surface tension of the colored dispersion according to this embodiment at 25°C is preferably about 20 to 55 mN / m when measured by the plate method. In practice, the appropriate physical properties are adjusted considering the ejection volume, response speed, ink droplet flight characteristics, etc., of the inkjet printer used.

[0110] The colored dispersion according to this embodiment can be used in various fields, but it is particularly preferable to use it as an ink for inkjet printing.

[0111] The colored dispersion according to this embodiment effectively suppresses the aggregation of particles in the colored dispersion during storage, which increases the average particle size, and also effectively suppresses the sedimentation of particles during storage. In other words, the colored dispersion according to this embodiment can stably maintain the dispersion state of particles in the colored dispersion. Furthermore, the colored dispersion according to this embodiment has low odor and excellent workability. Moreover, the colored dispersion according to this embodiment has superior redispersibility after drying compared to colored dispersions containing styrene-(meth)acrylic copolymer as a dispersant. Therefore, when the colored dispersion according to this embodiment is used as an ink, even if aggregated thickened material is generated due to the drying of the ink and temporarily causes nozzle clogging of the inkjet printer, the aggregated thickened material is redispersed by the subsequent ink, and the nozzle clogging is easily resolved.

[0112] In addition, colored products colored using the colored dispersion according to this embodiment exhibit excellent fastness in various aspects such as lightfastness, weather resistance, moisture resistance, and washability, as well as excellent color development, color reproduction, and water resistance.

[0113] <Colored Dispersion Set> The colored dispersion set according to this embodiment comprises the colored dispersion according to this embodiment and at least one other colored dispersion with a different hue from the colored dispersion. The colored dispersion according to this embodiment and the other colored dispersion may each contain two or more types with different hues.

[0114] <Recording media> The recording medium according to this embodiment is one to which the colored dispersion according to this embodiment, or each of the colored dispersions included in the colored dispersion set according to this embodiment, is attached.

[0115] Examples of recording media include information transmission sheets such as plain paper, resin-coated paper, inkjet paper, glossy paper, glossy film, and electrophotographic paper; fibers, fabrics; glass; metal; ceramics; leather; and substrates for color filters. While sheet-like recording media are preferred, three-dimensional shapes such as spheres and rectangular prisms may also be used.

[0116] Preferred recording media for inkjet printing include, for example, those with an ink-receiving layer provided on a substrate such as paper, synthetic paper, or film. The ink-receiving layer is provided by methods such as impregnating or coating the substrate with a cationic polymer; or coating the substrate surface with inorganic fine particles capable of absorbing pigments in a color dispersion of porous silica, alumina sol, or special ceramics, together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone. Recording media with such an ink-receiving layer are usually referred to as inkjet-specific paper (film), glossy paper (film), etc. Among these, inkjet-specific paper of the type in which inorganic fine particles capable of absorbing pigments in a color dispersion of porous silica, alumina sol, or special ceramics are coated on the substrate surface is considered to be particularly susceptible to oxidizing gases in the air, such as ozone gas. Representative examples of commercially available specialized paper include Canon Inc.'s "Photo Paper Glossy Pro Platinum Grade" and "Photo Paper Glossy Gold"; Seiko Epson Corporation's "Photo Paper Crispia (High Gloss)," "Photo Paper (Glossy)," and "Photo Matte Paper"; Hewlett-Packard Japan's "Advanced Photo Paper (Glossy)"; and Brother Corporation's "Premium Plus Glossy Photo Paper." Of course, plain paper can also be used, specifically Canon Inc.'s "PB Paper GF500" and Seiko Epson Corporation's "Double-Sided Premium Plain Paper" and "PPC (Plain Paper Copy) Paper."

[0117] Furthermore, fibers are preferred recording media for inkjet recording. Among fibers, hydrophobic fibers are preferred. Examples of hydrophobic fibers include polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, polyamide fibers, and blended fibers using two or more of these fibers. Blended fibers of these hydrophobic fibers with regenerated fibers such as rayon, and natural fibers such as cotton, silk, and wool are also included in the definition of hydrophobic fibers in this specification. Fiber structures (such as fabrics) are also included as fibers.

[0118] <Dyeing method for hydrophobic fibers> The method for printing hydrophobic fibers according to this embodiment is a method for printing hydrophobic fibers using a colored dispersion or a colored dispersion set according to this embodiment. Methods for printing hydrophobic fibers are broadly classified into direct printing methods and sublimation transfer methods.

[0119] The direct printing method includes a printing step of obtaining recorded images such as characters and patterns by attaching droplets of a colored dispersion to hydrophobic fibers using an inkjet printer or the like; a fixing step of fixing the water-insoluble dye in the colored dispersion attached to the hydrophobic fibers in the printing step to the hydrophobic fibers by heat; and a washing step of washing away any unfixed water-insoluble dye remaining in the hydrophobic fibers.

[0120] The fixing process is generally carried out by known steaming or baking. Steaming methods include, for example, treating hydrophobic fibers with a high-temperature steamer at 170-180°C for about 10 minutes, or with a high-pressure steamer at 120-130°C for about 20 minutes, thereby dyeing the hydrophobic fibers with water-insoluble dyes (also called wet heat fixing). Baking (thermosol) methods include, for example, treating hydrophobic fibers at 190-210°C for about 6-120 seconds, thereby dyeing the hydrophobic fibers with water-insoluble dyes (also called dry heat fixing).

[0121] The washing process involves washing the obtained fibers with hot water and, if necessary, with water. The hot water and water used for washing may contain surfactants. It is also preferable to dry the hydrophobic fibers after washing at a temperature of 50 to 120°C for 5 to 30 minutes.

[0122] On the other hand, the sublimation transfer method includes a printing step in which droplets of a colored dispersion are attached to an intermediate recording medium using an inkjet printer or the like to obtain a recorded image such as characters or patterns, and a transfer step in which hydrophobic fibers are brought into contact with the surface on which the colored dispersion is attached to the intermediate recording medium and heat-treated to transfer the recorded image to the hydrophobic fibers.

[0123] As an intermediate recording medium, it is preferable that the water-insoluble dye in the attached color dispersion does not aggregate on its surface and does not interfere with the sublimation of the water-insoluble dye when transferring the recorded image to the hydrophobic fibers. An example of such an intermediate recording medium is paper in which an ink-receiving layer is formed on the surface of inorganic fine particles such as silica, and inkjet-specific paper can be used.

[0124] The heat treatment used in the transfer process typically involves dry heat treatment at around 190-200°C.

[0125] The method for printing hydrophobic fibers according to this embodiment may further include a pretreatment step for hydrophobic fibers in order to prevent bleeding, etc. This pretreatment step may include applying an aqueous solution (pretreatment solution) containing a sizing agent, an alkaline substance, a reduction inhibitor, and a hydrotropic agent to the hydrophobic fibers before the color dispersion is applied.

[0126] Examples of adhesives include natural gums such as guar and locust bean; starches; sodium alginate and seaweed such as funori; plant peels such as pectin; cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose; modified starches such as carboxymethyl starch; and synthetic adhesives such as polyvinyl alcohol and polyacrylic acid esters, with sodium alginate being preferred.

[0127] Examples of alkaline substances include alkali metal salts of inorganic or organic acids; salts of alkaline earth metals; compounds that release alkali when heated; and alkali metal hydroxides and alkali metal salts are preferred. Specific examples include alkali metal hydroxides such as sodium hydroxide and calcium hydroxide; alkali metal salts of inorganic compounds such as sodium carbonate, sodium bicarbonate, potassium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, and sodium phosphate; and alkali metal salts of organic compounds such as sodium formate and sodium trichloroacetate; with sodium bicarbonate being preferred.

[0128] Sodium metanitrobenzenesulfonate is preferred as the reduction inhibitor. Examples of hydrotropic agents include urea, dimethylurea, and other urea derivatives, with urea being preferred.

[0129] The adhesive, alkaline substance, reduction inhibitor, and hydrotropic agent may be used individually or in combination of two or more types.

[0130] The mixing ratio of each component in the pretreatment solution is, for example, 0.5-5% by mass of the thickener, 0.5-5% by mass of sodium bicarbonate, 0-5% by mass of sodium metanitrobenzenesulfonate, 1-20% by mass of urea, and the remainder being water.

[0131] One method for applying the pretreatment solution to the hydrophobic fibers is the padding method. The padding ratio is preferably around 40-90%, and more preferably around 60-80%. [Examples]

[0132] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified in the examples, "parts," "%," and "ppm" all refer to mass. Furthermore, the aqueous dispersion and ink in the examples are both included in the above-mentioned colored dispersion.

[0133] <Preparation Example 1: Preparation of Aromatic Sulfonic Acid Formalin Condensate-Based Dispersant 1> Naphthalene (80 parts), 1-methylnaphthalene (335 parts), 2-methylnaphthalene (335 parts), and 1,5-dimethylnaphthalene (250 parts) were charged into a reaction vessel along with 98% sulfuric acid (1015 parts), and the mixture was heated at 158-162°C for 1.5 hours to carry out sulfonation. Next, water (300 parts) was added to the reaction mixture to dilute it, and then formalin (formaldehyde content: 35%) (670 parts) was added, and a condensation reaction was carried out at 100-110°C for 10 hours.

[0134] Next, water (1300 parts) was added to the reaction mixture, followed by the addition of liquid caustic soda (NaOH content: 48%) (650 parts) and slaked lime (Ca(OH)2) to adjust the pH to 11.8. The mixture was then alkalized at 80°C for 1 hour. Afterward, the reaction mixture was centrifuged and filtered to remove the salts such as gypsum and sodium sulfate produced during alkalization. The pH of the reaction mixture at this time was 11.8.

[0135] Next, formaldehyde was removed from this reaction mixture at 80°C for 1 hour while adding slaked lime to maintain a pH of 11.8. After that, the pH was adjusted to 6.5 using 98% sulfuric acid. The formaldehyde content of the obtained naphthalene sulfonic acid formalin condensate was 50 ppm. Then, the solvent was removed using an evaporator until the solid content was 40% (80°C, 50 mbar) to obtain aromatic sulfonic acid formalin condensate-based dispersant 1 (hereinafter also referred to as "dispersant 1").

[0136] <Preparation Example 2: Preparation of Aromatic Sulfonic Acid Formalin Condensate-Based Dispersant 2> 600 parts of deionized water were placed in a container, and while stirring at 400 rpm using a three-one motor, 400 parts of dispersant MF (manufactured by Anyang Double Circle Auxiliary CO., LTD) were added little by little. After the addition was complete, stirring was continued for 2 hours to confirm that there were no undissolved particles, and an aromatic sulfonic acid formalin condensate-based dispersant 2 (hereinafter also referred to as "dispersant 2") with a solid content of 40% was obtained.

[0137] <Preparation Example 3: Preparation of Aromatic Sulfonic Acid Formalin Condensate-Based Dispersant 3> 1,5-dimethylnaphthalene (1000 parts) and 98% sulfuric acid (1015 parts) were charged into a reaction vessel and heated at 158-162°C for 1.5 hours to carry out sulfonation. Next, water (300 parts) was added to this reaction mixture to dilute it, and then formalin (formaldehyde content: 35%) (670 parts) was added, and a condensation reaction was carried out at 100-110°C for 10 hours.

[0138] Next, water (1300 parts) was added to the reaction mixture, followed by the addition of liquid caustic soda (NaOH content: 48%) (650 parts) and slaked lime (Ca(OH)2) to adjust the pH to 11.8. Alkalination was then carried out at 80°C for 1 hour. Subsequently, the reaction mixture was centrifuged and filtered to remove salts such as gypsum and sodium sulfate produced during alkalization. The pH of the reaction mixture at this time was 11.8.

[0139] Next, formaldehyde was removed from this reaction mixture at 80°C for 1 hour while adding slaked lime to maintain a pH of 11.8. After that, the pH was adjusted to 9.4 using 98% sulfuric acid. The formaldehyde content of the obtained naphthalene sulfonic acid formalin condensate was 50 ppm. The solvent was then removed using an evaporator until the solid content was 40% (80°C, 50 mbar) to obtain aromatic sulfonic acid formalin condensate-based dispersant 3 (hereinafter also referred to as "dispersant 3").

[0140] <Preparation Example 4: Preparation of Aromatic Sulfonic Acid Formalin Condensate-Based Dispersant 4> Naphthalene (80 parts), 1-methylnaphthalene (620 parts), 1,5-dimethylnaphthalene (250 parts), and biphenyl (50 parts) were charged with 98% sulfuric acid (1015 parts) in a reaction vessel, and the mixture was heated at 158-162°C for 1.5 hours to carry out sulfonation. Next, water (300 parts) was added to this reaction mixture to dilute it, and then formalin (formaldehyde content: 35%) (670 parts) was added, and a condensation reaction was carried out at 100-110°C for 10 hours.

[0141] Next, water (1300 parts) was added to the reaction mixture, followed by the addition of liquid caustic soda (NaOH content: 48%) (650 parts) and slaked lime (Ca(OH)2) to adjust the pH to 11.8. The mixture was then alkalized at 80°C for 1 hour. Afterward, the reaction mixture was centrifuged and filtered to remove the salts such as gypsum and sodium sulfate produced during alkalization. The pH of the reaction mixture at this time was 11.8.

[0142] Next, formaldehyde was removed from this reaction mixture at 80°C for 1 hour while adding slaked lime to maintain a pH of 11.8. After that, the pH was adjusted to 9.4 using 98% sulfuric acid. The formaldehyde content of the obtained naphthalene sulfonic acid formalin condensate was 50 ppm. The solvent was then removed using an evaporator until the solid content was 40% (80°C, 50 mbar) to obtain aromatic sulfonic acid formalin condensate-based dispersant 4 (hereinafter also referred to as "dispersant 4").

[0143] <Preparation Example 5: Preparation of Aromatic Sulfonic Acid Formalin Condensate-Based Dispersant 5> Naphthalene (350 parts), 1-methylnaphthalene (450 parts), and 1,5-dimethylnaphthalene (200 parts) were charged into a reaction vessel along with 98% sulfuric acid (1015 parts), and the mixture was heated at 158-162°C for 1.5 hours to carry out sulfonation. Next, water (300 parts) was added to dilute the reaction mixture, and then formalin (formaldehyde content: 35%) (670 parts) was added, and a condensation reaction was carried out at 100-110°C for 10 hours.

[0144] Next, water (1300 parts) was added to the reaction mixture, followed by the addition of liquid caustic soda (NaOH content: 48%) (650 parts) and slaked lime (Ca(OH)2) to adjust the pH to 11.8. The mixture was then alkalized at 80°C for 1 hour. Afterward, the reaction mixture was centrifuged and filtered to remove the salts such as gypsum and sodium sulfate produced during alkalization. The pH of the reaction mixture at this time was 11.8.

[0145] Next, formaldehyde was removed from this reaction mixture at 80°C for 1 hour while adding slaked lime to maintain a pH of 11.8. After that, the pH was adjusted to 9.4 using 98% sulfuric acid. The formaldehyde content of the obtained naphthalene sulfonic acid formalin condensate was 50 ppm. The solvent was then removed using an evaporator until the solid content was 40% (80°C, 50 mbar) to obtain aromatic sulfonic acid formalin condensate-based dispersant 5 (hereinafter also referred to as "dispersant 5").

[0146] <Preparation Example 6: Preparation of Aromatic Sulfonic Acid Formalin Condensate-Based Dispersant 6> Naphthalene (450 parts), 1-methylnaphthalene (350 parts), and 1,5-dimethylnaphthalene (200 parts) were charged into a reaction vessel along with 98% sulfuric acid (1015 parts), and the mixture was heated at 158-162°C for 1.5 hours to carry out sulfonation. Next, water (300 parts) was added to this reaction mixture to dilute it, and then formalin (formaldehyde content: 35%) (670 parts) was charged, and a condensation reaction was carried out at 100-110°C for 10 hours.

[0147] Next, water (1300 parts) was added to the reaction mixture, followed by the addition of liquid caustic soda (NaOH content: 48%) (650 parts) and slaked lime (Ca(OH)2) to adjust the pH to 11.8. The mixture was then alkalized at 80°C for 1 hour. Afterward, the reaction mixture was centrifuged and filtered to remove the salts such as gypsum and sodium sulfate produced during alkalization. The pH of the reaction mixture at this time was 11.8.

[0148] Next, formaldehyde was removed from this reaction mixture at 80°C for 1 hour while adding slaked lime to maintain a pH of 11.8. After that, the pH was adjusted to 9.4 using 98% sulfuric acid. The formaldehyde content of the obtained naphthalene sulfonic acid formalin condensate was 50 ppm. The solvent was then removed using an evaporator until the solid content was 40% (80°C, 50 mbar) to obtain aromatic sulfonic acid formalin condensate-based dispersant 6 (hereinafter also referred to as "dispersant 6").

[0149] <Preparation Example 7: Preparation of Aromatic Sulfonic Acid Formalin Condensate-Based Dispersant 7> Naphthalene (100 parts), 1-methylnaphthalene (800 parts), and 1,5-dimethylnaphthalene (100 parts) were charged into a reaction vessel along with 98% sulfuric acid (1015 parts), and the mixture was heated at 158-162°C for 1.5 hours to carry out sulfonation. Next, water (300 parts) was added to this reaction mixture to dilute it, and then formalin (formaldehyde content: 35%) (670 parts) was added, and a condensation reaction was carried out at 100-110°C for 10 hours.

[0150] Next, water (1300 parts) was added to the reaction mixture, followed by the addition of liquid caustic soda (NaOH content: 48%) (650 parts) and slaked lime (Ca(OH)2) to adjust the pH to 11.8. The mixture was then alkalized at 80°C for 1 hour. Afterward, the reaction mixture was centrifuged and filtered to remove the salts such as gypsum and sodium sulfate produced during alkalization. The pH of the reaction mixture at this time was 11.8.

[0151] Next, formaldehyde was removed from the reaction mixture at 80°C for 1 hour while adding slaked lime to maintain a pH of 11.8. After that, the pH was adjusted to 9.4 using 98% sulfuric acid. The formaldehyde content of the obtained naphthalene sulfonic acid formalin condensate was 50 ppm. The solvent was then removed using an evaporator until the solid content was 40% (80°C, 50 mbar) to obtain aromatic sulfonic acid formalin condensate-based dispersant 7 (hereinafter also referred to as "dispersant 7").

[0152] <Preparation Example 8: Preparation of Aromatic Sulfonic Acid Formalin Condensate-Based Dispersant 8> Naphthalene (100 parts), 1-methylnaphthalene (350 parts), and 1,5-dimethylnaphthalene (550 parts) were charged into a reaction vessel along with 98% sulfuric acid (1015 parts), and the mixture was heated at 158-162°C for 1.5 hours to carry out sulfonation. Next, water (300 parts) was added to dilute the reaction mixture, and then formalin (formaldehyde content: 35%) (670 parts) was added, and a condensation reaction was carried out at 100-110°C for 10 hours.

[0153] Next, water (1300 parts) was added to the reaction mixture, followed by the addition of liquid caustic soda (NaOH content: 48%) (650 parts) and slaked lime (Ca(OH)2) to adjust the pH to 11.8. The mixture was then alkalized at 80°C for 1 hour. Afterward, the reaction mixture was centrifuged and filtered to remove the salts such as gypsum and sodium sulfate produced during alkalization. The pH of the reaction mixture at this time was 11.8.

[0154] Next, formaldehyde was removed from this reaction mixture at 80°C for 1 hour while adding slaked lime to maintain a pH of 11.8. After that, the pH was adjusted to 9.4 using 98% sulfuric acid. The formaldehyde content of the obtained naphthalene sulfonic acid formalin condensate was 50 ppm. The solvent was then removed using an evaporator until the solid content was 40% (80°C, 50 mbar) to obtain aromatic sulfonic acid formalin condensate-based dispersant 8 (hereinafter also referred to as "dispersant 8").

[0155] <Preparation Example 9: Preparation of Aromatic Sulfonic Acid Formalin Condensate-Based Dispersant 9> Naphthalene (100 parts), 1-methylnaphthalene (200 parts), and 1,5-dimethylnaphthalene (700 parts) were charged into a reaction vessel along with 98% sulfuric acid (1015 parts), and the mixture was heated at 158-162°C for 1.5 hours to carry out sulfonation. Next, water (300 parts) was added to this reaction mixture to dilute it, and then formalin (formaldehyde content: 35%) (670 parts) was added, and a condensation reaction was carried out at 100-110°C for 10 hours.

[0156] Next, water (1300 parts) was added to the reaction mixture, followed by the addition of liquid caustic soda (NaOH content: 48%) (650 parts) and slaked lime (Ca(OH)2) to adjust the pH to 11.8. The mixture was then alkalized at 80°C for 1 hour. Afterward, the reaction mixture was centrifuged and filtered to remove the salts such as gypsum and sodium sulfate produced during alkalization. The pH of the reaction mixture at this time was 11.8.

[0157] Next, formaldehyde was removed from the reaction mixture at 80°C for 1 hour while adding slaked lime to maintain a pH of 11.8. After that, the pH was adjusted to 9.4 using 98% sulfuric acid. The formaldehyde content of the obtained naphthalene sulfonic acid formalin condensate was 50 ppm. The solvent was then removed using an evaporator until the solid content was 40% (80°C, 50 mbar) to obtain aromatic sulfonic acid formalin condensate-based dispersant 9 (hereinafter also referred to as "dispersant 9").

[0158] <Preparation Example 10: Preparation of Aromatic Sulfonic Acid Formalin Condensate-Based Dispersant 10> Naphthalene (700 parts), 1-methylnaphthalene (210 parts), and 1,5-dimethylnaphthalene (90 parts) were charged into a reaction vessel along with 98% sulfuric acid (1015 parts), and the mixture was heated at 158-162°C for 1.5 hours to carry out sulfonation. Next, water (300 parts) was added to this reaction mixture to dilute it, and then formalin (formaldehyde content: 35%) (670 parts) was added, and a condensation reaction was carried out at 100-110°C for 10 hours.

[0159] Next, water (1300 parts) was added to the reaction mixture, followed by the addition of liquid caustic soda (NaOH content: 48%) (650 parts) and slaked lime (Ca(OH)2) to adjust the pH to 11.8. The mixture was then alkalized at 80°C for 1 hour. Afterward, the reaction mixture was centrifuged and filtered to remove the salts such as gypsum and sodium sulfate produced during alkalization. The pH of the reaction mixture at this time was 11.8.

[0160] Next, formaldehyde was removed from the reaction mixture at 80°C for 1 hour while adding slaked lime to maintain a pH of 11.8. After that, the pH was adjusted to 9.4 using 98% sulfuric acid. The formaldehyde content of the obtained naphthalene sulfonic acid formalin condensate was 50 ppm. The solvent was then removed using an evaporator until the solid content was 40% (80°C, 50 mbar) to obtain aromatic sulfonic acid formalin condensate-based dispersant 10 (hereinafter also referred to as "dispersant 10").

[0161] <Preparation Example 11: Preparation of Aromatic Sulfonic Acid Formalin Condensate-Based Dispersant 11> Naphthalene (600 parts), 1-methylnaphthalene (310 parts), and 1,5-dimethylnaphthalene (90 parts) were charged into a reaction vessel along with 98% sulfuric acid (1015 parts), and the mixture was heated at 158-162°C for 1.5 hours to carry out sulfonation. Next, water (300 parts) was added to this reaction mixture to dilute it, and then formalin (formaldehyde content: 35%) (670 parts) was added, and a condensation reaction was carried out at 100-110°C for 10 hours.

[0162] Next, water (1300 parts) was added to the reaction mixture, followed by the addition of liquid caustic soda (NaOH content: 48%) (650 parts) and slaked lime (Ca(OH)2) to adjust the pH to 11.8. The mixture was then alkalized at 80°C for 1 hour. Afterward, the reaction mixture was centrifuged and filtered to remove the salts such as gypsum and sodium sulfate produced during alkalization. The pH of the reaction mixture at this time was 11.8.

[0163] Next, formaldehyde was removed from the reaction mixture at 80°C for 1 hour while adding slaked lime to maintain a pH of 11.8. After that, the pH was adjusted to 9.4 using 98% sulfuric acid. The formaldehyde content of the obtained naphthalene sulfonic acid formalin condensate was 50 ppm. The solvent was then removed using an evaporator until the solid content was 40% (80°C, 50 mbar) to obtain aromatic sulfonic acid formalin condensate-based dispersant 11 (hereinafter also referred to as "dispersant 11").

[0164] <Preparation Example 12: Preparation of Aromatic Sulfonic Acid Formalin Condensate-Based Dispersant 12> Naphthalene (100 parts), 1-methylnaphthalene (850 parts), and 1,5-dimethylnaphthalene (50 parts) were charged into a reaction vessel along with 98% sulfuric acid (1015 parts), and the mixture was heated at 158-162°C for 1.5 hours to carry out sulfonation. Next, water (300 parts) was added to the reaction mixture to dilute it, and then formalin (formaldehyde content: 35%) (670 parts) was added, and a condensation reaction was carried out at 100-110°C for 10 hours.

[0165] Next, water (1300 parts) was added to the reaction mixture, followed by the addition of liquid caustic soda (NaOH content: 48%) (650 parts) and slaked lime (Ca(OH)2) to adjust the pH to 11.8. The mixture was then alkalized at 80°C for 1 hour. Afterward, the reaction mixture was centrifuged and filtered to remove the salts such as gypsum and sodium sulfate produced during alkalization. The pH of the reaction mixture at this time was 11.8.

[0166] Next, formaldehyde was removed from the reaction mixture at 80°C for 1 hour while adding slaked lime to maintain a pH of 11.8. After that, the pH was adjusted to 9.4 using 98% sulfuric acid. The formaldehyde content of the obtained naphthalene sulfonic acid formalin condensate was 50 ppm. The solvent was then removed using an evaporator until the solid content was 40% (80°C, 50 mbar) to obtain aromatic sulfonic acid formalin condensate-based dispersant 12 (hereinafter also referred to as "dispersant 12").

[0167] The compositions of the dispersants 1 to 12 obtained in Preparation Examples 1 to 12 are shown in Table 1 below.

[0168] [Table 1]

[0169] <Examples 1-20, Comparative Examples 1-7: Preparation of Aqueous Dispersions 1-27> 0.2 mm diameter glass beads were added to mixtures of each component listed in Tables 2-5 below, and the mixtures were dispersed in a sand mill under water cooling for approximately 15 hours. The resulting liquids were filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC, pore size: 0.5 μm) to obtain aqueous dispersions. In Tables 2-5, the values ​​for each component indicate the amount added.

[0170] [Table 2]

[0171] [Table 3]

[0172] [Table 4]

[0173] [Table 5]

[0174] The abbreviations in Tables 2-5 represent the following: DY54: CI Disperse Yellow 54 DR60: CI Disperse Thread 60 DB359: CI Disperse Blue 359 DB360: CI Disperse Blue 360 DOr25: CI Disperse Orange 25 SOr60: CI Solvent Orange 60 Labelin W-40: Labelin W-40 (aqueous solution of 40% solids of creosote oil sulfonate sodium formalin condensate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Labelin FD40: Labelin FD40 (aqueous solution of sodium naphthalene sulfonate formalin condensate with 40% solids, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Demol N: Demol N (β-methylnaphthalene sulfonate sodium formalin condensate, 40% solids aqueous solution, manufactured by Kao Corporation) BPS-30: Nikkol BPS-30 (ethylene oxide adduct of phytosterol, manufactured by Nikko Chemicals Co., Ltd.) Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza Corporation) Surfinol 104PG50: Surfinol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted to a 50% concentration with propylene glycol.

[0175] <Examples 21-38, Comparative Examples 8-14: Preparation of Inks 1-25> The aqueous dispersions 1 to 27 obtained in Examples 1 to 20 and Comparative Examples 1 to 7 were mixed with the respective components listed in Tables 6 to 9 below, stirred for 30 minutes, and then filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC, pore size: 0.5 μm) to prepare inks 1 to 25. In Tables 6 to 9, the numerical values ​​for each component indicate the number of copies added.

[0176] [Table 6]

[0177] [Table 7]

[0178] [Table 8]

[0179] [Table 9]

[0180] The abbreviations in Tables 6-9 represent the following: BYK-348: Polyether-modified polydimethylsiloxane (BYK-348, manufactured by BYC Chemie Japan Co., Ltd.) TEA-80: Triethanolamine (TEA-80, manufactured by Oxalis Chemicals Co., Ltd.) Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza Corporation)

[0181] <Examples 39-49: Preparation of aqueous dispersions 28-38> 0.2 mm diameter glass beads were added to the mixtures of each component listed in Tables 10-11 below, and the mixtures were dispersed in a sand mill under water cooling for approximately 15 hours. The resulting liquid was filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC, pore size: 0.5 μm) to obtain each aqueous dispersion. In Tables 10-11, the values ​​for each component indicate the amount added.

[0182] [Table 10]

[0183] [Table 11]

[0184] The abbreviations in Tables 10-11 represent the following: DY54: CI Disperse Yellow 54 DR60: CI Disperse Thread 60 DB359: CI Disperse Blue 359 DB360: CI Disperse Blue 360 DOr25: CI Disperse Orange 25 SOr60: CI Solvent Orange 60 DR92: CI Disperse Thread 92 DOr73: CI Disperse Orange 73 BPS-30: Nikkol BPS-30 (ethylene oxide adduct of phytosterol, manufactured by Nikko Chemicals Co., Ltd.) Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza Corporation) Surfinol 104PG50: Surfinol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted to a 50% concentration with propylene glycol.

[0185] <Examples 50-64: Preparation of inks 26-40> The aqueous dispersions 28-38 obtained in Examples 39-49 were mixed with the components listed in Tables 12-14 below, stirred for 30 minutes, and then filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC, pore size: 0.5 μm) to prepare inks 26-40, respectively. In Tables 12-14, the values ​​for each component indicate the number of copies added.

[0186] [Table 12]

[0187] [Table 13]

[0188] [Table 14]

[0189] The abbreviations in Tables 12-14 represent the following: BYK-348: Polyether-modified polydimethylsiloxane (BYK-348, manufactured by BYC Chemie Japan Co., Ltd.) TEA-80: Triethanolamine (TEA-80, manufactured by Oxalis Chemicals Co., Ltd.) Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza Corporation)

[0190] <Examples 65-67: Preparation of aqueous dispersions 39-41> A mixture of each component listed in Table 15 below was mixed with 0.2 mm diameter glass beads and dispersed in a sand mill under water cooling for approximately 15 hours. The resulting liquid was filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC, pore size: 0.5 μm) to obtain each aqueous dispersion. In Table 15, the values ​​for each component indicate the amount added.

[0191] [Table 15]

[0192] In Table 15, each abbreviation represents the following: DY54: CI Disperse Yellow 54 DR60: CI Disperse Thread 60 DB359: CI Disperse Blue 359 DB360: CI Disperse Blue 360 DOr25: CI Disperse Orange 25 SOr60: CI Solvent Orange 60 Labelin W-40: Labelin W-40 (aqueous solution of 40% solids of creosote oil sulfonate sodium formalin condensate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Labelin FD40: Labelin FD40 (aqueous solution of sodium naphthalene sulfonate formalin condensate with 40% solids, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Demol N: Demol N (β-methylnaphthalene sulfonate sodium formalin condensate, 40% solids aqueous solution, manufactured by Kao Corporation) BPS-30: Nikkol BPS-30 (ethylene oxide adduct of phytosterol, manufactured by Nikko Chemicals Co., Ltd.) Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza Corporation) Surfinol 104PG50: Surfinol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted to a 50% concentration with propylene glycol.

[0193] <Examples 68-70: Preparation of inks 41-43> The aqueous dispersions 39-41 obtained in Examples 65-67 were mixed with the components listed in Table 16 below, stirred for 30 minutes, and then filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC, pore size: 0.5 μm) to prepare inks 41-43, respectively. In Table 16, the numerical values ​​for each component indicate the number of copies added.

[0194] [Table 16]

[0195] In Table 16, each abbreviation represents the following: BYK-348: Polyether-modified polydimethylsiloxane (BYK-348, manufactured by BYC Chemie Japan Co., Ltd.) TEA-80: Triethanolamine (TEA-80, manufactured by Oxalis Chemicals Co., Ltd.) Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza Corporation)

[0196] <Rating> The following evaluation tests were conducted using the aqueous dispersions 1-41 and inks 1-43 prepared as described above. The results are shown in Tables 2-16 above.

[0197] [Initial viscosity of aqueous dispersion] The initial viscosity of each aqueous dispersion was measured at 25°C using an E-type viscometer calibrated with JS10 viscometer calibration standard solution (manufactured by Nippon Grease Co., Ltd.), and evaluated according to the following criteria. A or B indicates a good evaluation, and C indicates a poor evaluation. -Evaluation Criteria- A: Initial viscosity is between 2 mPa·s and less than 10 mPa·s B: Initial viscosity is between 10 mPa·s and less than 80 mPa·s C: Initial viscosity is 80 mPa·s or higher

[0198] [Viscosity change test of aqueous dispersion] The viscosity over time of each aqueous dispersion, stored at 60°C for 5 days, was measured at 25°C using an E-type viscometer calibrated with JS10 viscometer calibration standard solution (manufactured by Nippon Grease Co., Ltd.), and evaluated according to the following criteria. A or B indicates a good evaluation, and C indicates a poor evaluation. -Evaluation Criteria- A: Viscosity over time is between 2 mPa·s and less than 10 mPa·s B: Viscosity over time is between 10 mPa·s and 80 mPa·s. C: Viscosity over time is 80 mPa·s or higher

[0199] [Initial viscosity of ink] The initial viscosity of each ink was measured at 25°C using an E-type viscometer calibrated with JS10 viscometer calibration standard solution (manufactured by Nippon Grease Co., Ltd.), and evaluated according to the following criteria. A or B indicates a good evaluation, and C indicates a poor evaluation. -Evaluation Criteria- A: Initial viscosity is between 2 mPa·s and less than 4 mPa·s B: Initial viscosity is between 4 mPa·s and less than 5 mPa·s C: Initial viscosity of 5 mPa·s or higher

[0200] [Ink viscosity change test] The viscosity of each ink, stored at 60°C for 5 days, was measured at 25°C using an E-type viscometer calibrated with JS10 viscometer calibration standard solution (manufactured by Nippon Grease Co., Ltd.), and evaluated according to the following criteria. A or B indicates a good evaluation, and C indicates a poor evaluation. -Evaluation Criteria- A: Viscosity over time is between 2 mPa·s and less than 4 mPa·s. B: Viscosity over time is between 4 mPa·s and 5 mPa·s. C: Viscosity over time is 5 mPa·s or higher

[0201] [Particle size change test] Each aqueous composition or ink, stored at 60°C for 5 days, was diluted 500-fold with water. The median diameter (D50, volume-average particle size) of the colorant was measured using a Nanotrac Wave-EX150 (manufactured by Microtrac-Bell Co., Ltd.) and evaluated according to the following criteria. S, A, or B indicates a good evaluation, and C indicates a poor evaluation. -Evaluation Criteria- S:D50 is less than 120nm A:D50 is between 120nm and 140nm B:D50 is between 140nm and less than 170nm C:D50 is 170nm or higher

[0202] [Odor test] Each color dispersion or ink was placed in a 50 mL I-Boy wide-mouth bottle (manufactured by AS ONE Corporation) and sealed. After being stored at 60°C for 5 hours, the lid was opened, and the odor at a distance of 5 cm from the opening of the I-Boy wide-mouth bottle (temperature: 25°C) was checked by 10 evaluators and evaluated according to the following criteria. A or B indicates a good evaluation, and C or D indicates a poor evaluation. -Evaluation Criteria- A: More than 8 people did not perceive any unpleasant odor. B: Six to seven people did not perceive any unpleasant odor. C: 3 to 5 people do not perceive any unpleasant odor. D: Two or fewer people do not perceive any unpleasant odors.

[0203] [Ink settling test A (inks 1-10, 26-32, and 41-43)] The sedimentation rate was calculated using the following formula, based on the absorbance Abs1 at the maximum absorption wavelength (λmax) around 574 nm, measured during ink preparation, and the absorbance Abs2 at the maximum absorption wavelength (λmax) around 574 nm, measured after separating the supernatant of the ink stored at 60°C for 5 days. The absorbance was measured using a UV-Vis spectrophotometer (UV-2550, Shimadzu Corporation) after diluting the ink 2000 times with deionized water. Settlement rate (%) = {(Abs1 - Abs2) / Abs1} × 100 The calculated settlement rate was then evaluated according to the following criteria: S, A, or B indicates a good evaluation, while C indicates a poor evaluation. -Evaluation Criteria- S: Settlement rate less than 5% A: Settlement rate is 5% or more but less than 10% B: Settlement rate is 10% or more but less than 15% C: Settlement rate of 15% or more

[0204] [Ink sedimentation test B (inks 11-12)] The sedimentation rate was calculated using the following formula, based on the absorbance Abs3 at the maximum absorption wavelength (λmax) around 408 nm, measured during ink preparation, and the absorbance Abs4 at the maximum absorption wavelength (λmax) around 408 nm, measured after separating the supernatant of the ink stored at 60°C for 5 days. The absorbance was measured using a UV-Vis spectrophotometer (UV-2550, Shimadzu Corporation) after diluting the ink 2000 times with deionized water. Settlement rate (%) = {(Abs3 - Abs4) / Abs3} × 100 The calculated settlement rate was then evaluated according to the following criteria: S, A, or B indicates a good evaluation, while C indicates a poor evaluation. -Evaluation Criteria- S: Settlement rate less than 5% A: Settlement rate is 5% or more but less than 10% B: Settlement rate is 10% or more but less than 15% C: Settlement rate of 15% or more

[0205] [Ink sedimentation test C (inks 13-14)] The sedimentation rate was calculated using the absorbance Abs5 at the maximum absorption wavelength (λmax) around 574 nm, measured during ink preparation, and the absorbance Abs6 at the maximum absorption wavelength (λmax) around 574 nm, measured after separating the supernatant of the ink stored at 60°C for 5 days, according to the following formula. The absorbance was measured using a UV-Vis spectrophotometer (UV-2550, Shimadzu Corporation) after diluting the ink 2000 times with deionized water. Settlement rate (%) = {(Abs5 - Abs6) / Abs5} × 100 Then, the calculated sedimentation rate was evaluated according to the following criteria. S, A, or B indicates good evaluation, and C indicates poor evaluation. - Evaluation Criteria - S: Sedimentation rate is less than 5% A: Sedimentation rate is 5% or more and less than 10% B: Sedimentation rate is 10% or more and less than 15% C: Sedimentation rate is 15% or more

[0206] [Ink Sedimentation Test D (Inks 15 - 16 and Inks 33 - 36)] Using the absorbance Abs7 at the maximum absorption wavelength (λmax) near 420 nm measured during ink preparation and the absorbance Abs8 at the maximum absorption wavelength (λmax) near 420 nm measured by collecting the supernatant of the ink stored at 60°C for 5 days, the sedimentation rate was calculated according to the following formula. The absorbance was measured using an ultraviolet-visible spectrophotometer (UV-2550, manufactured by Shimadzu Corporation) after adding ion-exchanged water to the ink and diluting it 2000 times. Sedimentation rate (%) = {(Abs7 - Abs8) / Abs7} × 100 Then, the calculated sedimentation rate was evaluated according to the following criteria. S, A, or B indicates good evaluation, and C indicates poor evaluation. - Evaluation Criteria - S: Sedimentation rate is less than 5% A: Sedimentation rate is 5% or more and less than 10% B: Sedimentation rate is 10% or more and less than 15% C: Sedimentation rate is 15% or more

[0207] [Ink Sedimentation Test E (Inks 17 - 18 and Inks 37 - 40)] Using the absorbance Abs9 at the maximum absorption wavelength (λmax) near 574 nm measured during ink preparation and the absorbance Abs 10 at the maximum absorption wavelength (λmax) near 574 nm measured by collecting the supernatant of the ink stored at 60°C for 5 days, the sedimentation rate was calculated according to the following formula. The absorbance was measured using an ultraviolet-visible spectrophotometer (UV-2550, manufactured by Shimadzu Corporation) after adding ion-exchanged water to the ink and diluting it 2000 times. Settlement rate (%) = {(Abs9 - Abs 10 ) / Abs9}×100 The calculated settlement rate was then evaluated according to the following criteria: S, A, or B indicates a good evaluation, while C indicates a poor evaluation. -Evaluation Criteria- S: Settlement rate less than 5% A: Settlement rate is 5% or more but less than 10% B: Settlement rate is 10% or more but less than 15% C: Settlement rate of 15% or more

[0208] As is clear from the results in Tables 2-16, aqueous dispersions 1-20 and 28-41, as well as inks 1-18 and 26-43 prepared using them, had low initial viscosity, did not significantly increase in viscosity or particle size even when stored at high temperatures, and had little unpleasant odor. Furthermore, inks 1-18 and 26-43 exhibited minimal particle sedimentation and excellent dispersion stability.

Claims

1. It contains a water-insoluble dye, an aromatic sulfonic acid formalin condensate-based dispersant, and water. The aforementioned aromatic sulfonic acid formalin condensate dispersant is a reaction product obtained by a condensation reaction between an aromatic sulfonic acid compound and formalin. The aforementioned aromatic sulfonic acid compound includes a compound represented by the following formulas (1) to (3): A colored dispersion in which, when the total amount of the aromatic sulfonic acid compounds is 100% by mass, the total amount of the compound represented by the following formula (2) and the compound represented by the following formula (3) is greater than 30% by mass and less than or equal to 95% by mass, and the total amount of the compound represented by the following formula (3) is greater than 5% by mass and less than 70% by mass. 【Chemistry 1】 (In the formula, M １ M ２ M ３ Each of these independently represents a hydrogen atom, a metal ion, or an ammonium ion.

2. The colored dispersion according to claim 1, wherein when the total amount of the aromatic sulfonic acid compounds is 100% by mass, the total amount of the compound represented by formula (2) and the compound represented by formula (3) is 40 to 95% by mass, and the total amount of the compound represented by formula (3) is 10 to 60% by mass.

3. The colored dispersion according to claim 1 or 2, wherein the aromatic sulfonic acid compound further comprises a compound represented by the following formula (4). 【Chemistry 2】 (In the formula, M ４ (This represents a hydrogen atom, a metal ion, or an ammonium ion.)

4. Furthermore, the colored dispersion according to claim 1 or 2 contains at least one selected from the group consisting of alkylene oxide adducts of phytosterols, alkylene oxide adducts of hydrogenated phytosterols, alkylene oxide adducts of cholestanol, and alkylene oxide adducts of hydrogenated cholestanol.

5. Furthermore, the colored dispersion according to claim 1 or 2 contains a polysiloxane compound.

6. Furthermore, the colored dispersion according to claim 1 or 2, further containing glycol ether.

7. The colored dispersion according to claim 1 or 2, wherein the average particle size of the water-insoluble dye is 60 to 200 nm.

8. A colored dispersion set comprising a colored dispersion according to claim 1 or 2, and at least one other colored dispersion having a different hue from the colored dispersion.

9. A recording medium to which the colored dispersion described in claim 1 or 2 is attached.

10. The recording medium according to claim 9, wherein the recording medium is a hydrophobic fiber.

11. A printing step of obtaining a recorded image by attaching droplets of the colored dispersion according to claim 1 or 2 to an intermediate recording medium, A method for printing with hydrophobic fibers, comprising a transfer step of bringing hydrophobic fibers into contact with the surface on which the droplets are attached in the intermediate recording medium and heat-treating them to transfer the recorded image to the hydrophobic fibers.

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