JP7795470B2 - Coloring liquid, coloring liquid set, printed matter, and method for printing hydrophobic fibers - Google Patents

Description

The present invention relates to a coloring liquid, a coloring liquid set using the same, a printed material, and a method for printing hydrophobic fibers.

In recent years, inkjet printing methods that do not require platemaking have been proposed, and inkjet printing is now being used to print fibers, including cloth. Compared to traditional printing methods such as screen printing, inkjet printing offers various advantages, including the absence of platemaking, resource and energy savings, and the ease of high-resolution expression. Hydrophobic fiber fabrics, such as polyester fibers, are generally dyed with water-insoluble colorants. Therefore, aqueous inks used to print hydrophobic fibers using inkjet printing methods generally require dispersion inks that disperse water-insoluble colorants in water and have good dispersion stability and other properties. Inkjet printing methods for hydrophobic fibers, such as polyester fibers, can be broadly divided into the following two methods. One method is the direct printing method, in which ink is applied (printed) directly to the fibers, and then the dye in the ink is dyed into the fibers by heat treatment such as high-temperature steaming. The other method is the sublimation transfer method, in which ink is applied (printed) to an intermediate recording medium (such as dedicated transfer paper), and then the ink-applied surface of the intermediate recording medium is superimposed on hydrophobic fibers, and the dye is transferred from the intermediate recording medium to the fibers by heat.

Of the above, the sublimation transfer method is mainly used for printing flags and other items, and the ink contains an easily sublimable dye that is highly transferable to polyester by heat treatment.
(1) Printing step: applying dye ink to an intermediate recording medium using an inkjet printer;
(2) Transfer step: A step of transferring and fixing the dye from the intermediate recording medium into the fiber by heat treatment.
Since commercially available transfer paper can be widely used, no pretreatment of the fabric is required and the washing step is omitted.

One of the performance requirements for inks used in inkjet textile printing is ink ejection stability. Inkjet printing requires that ink be ejected in small droplets from a thin nozzle, and colored liquids that do not experience ejection problems even during long periods of continuous operation and that can produce high-quality printed textiles are required. Patent Document 1 describes preparing ink by adding a water-soluble organic solvent as a humectant, a surfactant as a surface tension adjuster, and other additives (pH adjusters, antiseptics, antifungals, defoamers, etc.) to a dye dispersion liquid in which a water-insoluble colorant selected from disperse dyes and oil-soluble dyes is dispersed in water.

The performance requirements for water-insoluble colorants include good sublimation, high color development on hydrophobic fibers, and excellent fastness properties. Therefore, the number of dyes widely used on the market is limited, and each company has a similar color reproduction range. Inkjet printer inks and paints are known to express colors through subtractive color mixing, with the basic ink set consisting of a four-color ink consisting of the "three primary colors" of cyan, magenta, and yellow, plus black.

C.I. Disperse Blue 359 is known as a colorant used in cyan inks in dye sublimation transfer printing, and using C.I. Disperse Blue 359 can produce a high-saturation, beautiful blue hue. However, using the colorant alone presents the issue of poor ejection stability of the colored liquid, and improvements in ejection stability are needed.

WO 2005/121263

However, while combining colorants can suppress recrystallization of the colorant in the ink, preventing nozzle clogging during inkjet printing and improving ejection stability, it also results in a decrease in the color development and saturation of the resulting printed fabric when printing hydrophobic fibers. Therefore, it has been difficult to obtain a colorant solution that has the same color development as C.I. Disperse Blue 359, a colorant commonly used in cyan colorants, a wider color gamut than that colorant, and superior ejection stability.

The objective of the present invention is to provide a coloring liquid that has a wide range of hue expression in the cyan to blue region and has excellent color development and ejection stability.

As a result of extensive research, the present inventors have found that a water-insoluble colorant containing at least a water-insoluble colorant is
(a) Compound A, in which any one of the substituents R ¹ to R ⁶ in the following formula (1) is a cyano group and the other five are hydrogen atoms:
The present inventors have found that a colored liquid containing at least one compound selected from the group consisting of (b) a compound B in which at least two of the substituents R ¹ to R ⁶ in the following formula (1) are cyano groups and all of the substituents other than the cyano groups are hydrogen atoms, and a compound C in which the substituents R ¹ to R ⁶ in the following formula (1) are all hydrogen atoms, wherein the total mass X of (a) above and the total mass Y of (b) above satisfy the relationship X/Y≧7.4, solves the above problems, and have completed the present invention.

More specifically, by incorporating at least one compound selected from the group consisting of specific compounds B and C, each of which has an anthraquinone skeleton within its molecule, it is possible to specifically suppress crystal growth of the main colorant, compound A, thereby contributing to the storage stability of the colored liquid. Achieving this performance effectively prevents head filter and nozzle clogging when the colored liquid is used as ink in inkjet printers, thereby having a positive effect on the ejection stability of the ink.

To obtain printed textiles with high color development and saturation, it is preferable to use compound A alone. However, from the viewpoint of the above-mentioned ejection stability, it is necessary to add compound B and/or compound C. We have found that in order to prevent a decrease in the color development and saturation of printed textiles obtained from a coloring liquid using compound A, it is necessary to blend compound B and/or compound C in a specific ratio. This has enabled us to improve ejection stability and obtain printed textiles with high color development and saturation.

That is, the present invention relates to the following 1) to 12).

1)
The ink composition contains at least a water-insoluble colorant,
(a) Compound A, in which any one of the substituents R ¹ to R ⁶ in the following formula (1) is a cyano group and the other five are hydrogen atoms:
(b) A colored liquid containing at least one compound selected from the group consisting of: a compound B in which at least two of the substituents R ¹ to R ⁶ in the following formula (1) are cyano groups and all of the substituents other than the cyano groups are hydrogen atoms; and a compound C in which the substituents R ¹ to R ⁶ in the following formula (1) are all hydrogen atoms, wherein the total mass X of (a) above and the total mass Y of (b) above satisfy the relationship X/Y≧7.4.

2)
1) The colored liquid according to 1), wherein the compound A is a compound represented by the formula (1) in which the substituent R ¹ is a cyano group.
3)
The colored liquid according to 1) or 2), wherein the compound B is a compound represented by the formula (1) in which the substituents R ¹ and R ² are each a cyano group.
4)
The colored liquid according to any one of 1) to 3), further comprising a dispersant.
5)
4) The colored liquid according to 4), wherein the dispersant contains at least one selected from the group consisting of a styrene-(meth)acrylic copolymer, a formalin condensate of an aromatic sulfonic acid or a salt thereof, polyoxyethylene arylphenyl ether, polyoxyethylene arylphenyl ether sulfate, and polyoxyethylene naphthyl ether.
6)
6. The colored liquid according to 5), wherein the formalin condensate of aromatic sulfonic acid or its salt includes a formalin condensate of creosote oil sulfonic acid or its salt.
7)
6) The colored liquid according to 5) or 6), wherein the polyoxyethylene aryl phenyl ether is polyoxyethylene styryl phenyl ether, and/or the polyoxyethylene aryl phenyl ether sulfate is polyoxyethylene styryl phenyl ether sulfate.
8)
The coloring liquid according to any one of 1) to 7), further comprising a phytosterol-based compound.
9)
A coloring liquid set comprising the coloring liquid according to any one of 1) to 8) above and another coloring liquid.
10)
A recorded matter obtained by using the coloring liquid according to any one of 1) to 8) or the coloring liquid set according to 9) on a recording medium.
11)
10) The recorded matter according to 10), wherein the recording medium is a hydrophobic fiber.
12)
A method for printing hydrophobic fibers, comprising: a printing step of depositing droplets of the coloring liquid according to any one of 1) to 8) or the coloring liquid set according to 9) onto an intermediate recording medium to obtain a recorded image; and a transfer step of bringing hydrophobic fibers into contact with the surface of the intermediate recording medium onto which the droplets of the coloring liquid or the coloring liquid set have been deposited, and subjecting the fibers to a heat treatment to transfer the recorded image to the hydrophobic fibers.

The present invention makes it possible to obtain a colored liquid that has high color development and saturation, as well as excellent ejection stability.

The present invention will be described in detail below. In this specification, including the examples, all "parts" and "%" are by weight unless otherwise specified. Also, "C.I." is an abbreviation for Color Index.

The coloring liquid of the present invention contains at least a water-insoluble colorant, and the water-insoluble colorant is
(a) Compound A, in which any one of the substituents R ¹ to R ⁶ in the above formula (1) is a cyano group and the other five are hydrogen atoms;
(b) A colored liquid containing at least any compound selected from the group consisting of: Compound B, in which at least two of the substituents R ¹ to R ⁶ in the above formula (1) are cyano groups and all of the substituents other than the cyano groups are hydrogen atoms; and Compound C, in which the substituents R ¹ to R ⁶ in the above formula (1) are all hydrogen atoms, wherein the total mass X of (a) and the total mass Y of (b) satisfy the relationship X/Y≧7.4.

[Compound A]
The compound A is not particularly limited as long as it is a compound in which any one of the substituents R ¹ to R ⁶ in the formula (1) is a cyano group and the other five are hydrogen atoms, and it is preferable that R ¹ in the formula (1) is a cyano group. As the compound A, C.I. Disperse Blue 359 is preferable. The compound A may be used alone or in combination of two or more types.

[Compound B]
The compound B is not particularly limited as long as at least two of the substituents R ¹ to R ⁶ in the formula (1) are cyano groups and all of the substituents other than the cyano groups are hydrogen atoms, and it is preferable that R ¹ and R ² in the formula (1) are cyano groups. Compound B may be used alone or in combination of two or more types.

[Compound C]
The compound C is a compound in which all of R ¹ to R ⁶ in the formula (1) are hydrogen atoms.

Compound A of the compounds represented by formula (1) above can be obtained as a commercially available dye, such as the above-mentioned C.I. Disperse Blue 359. Compound B can be obtained, for example, by referring to Japanese Patent Publication No. 5-065358. Compound C can be obtained, for example, by referring to the non-patent document Zhurnal Organicheskoi Khimii, Volume 18, Issue 7, Pages 1539-49.

In the colored liquid, the total mass X of (a) and the total mass Y of (b) satisfy the relationship X/Y≧7.4, preferably X/Y≧10, and more preferably X/Y≧11. From the viewpoint of ejection stability, it is preferable that X/Y≦1000, more preferably X/Y≦500, even more preferably X/Y≦490, particularly preferably X/Y≦100, and extremely preferably X/Y≦60.
The content of the water-insoluble colorant in the colored liquid is preferably 0.01% or more and 40% or less, more preferably 0.1% or more and 20% or less, and even more preferably 0.5% or more and 15% or less.

The above coloring liquid may further contain a dispersant.

Examples of dispersants that can be used include styrene-(meth)acrylic copolymers, formalin condensates of aromatic sulfonic acids or their salts, polyoxyethylene arylphenyl ethers, polyoxyethylene phenyl ether sulfates, and polyoxyethylene naphthyl ethers. The styrene-(meth)acrylic copolymers are copolymers of styrene-based monomers and (meth)acrylic monomers. In this specification, "(meth)acrylic" refers to "acrylic" and/or "methacrylic." Specific examples of these 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-maleic acid (anhydride) copolymer, acrylic acid ester-maleic acid (anhydride) copolymer, (α-methyl)styrene-acrylic acid ester-maleic acid (anhydride) copolymer, acrylic acid ester-allylsulfonic acid ester copolymer, acrylic acid ester-styrene sulfonic acid copolymer, (α-methyl)styrene-methacrylic acid sulfonic acid copolymer, polyester-acrylic acid copolymer, polyester-acrylic acid-acrylic acid ester copolymer, polyester-methacrylic acid copolymer, polyester-methacrylic acid-acrylic acid ester copolymer; and the like. Among these, those in which the compound containing an aromatic hydrocarbon group is styrene are preferred. In this specification, (α-methyl)styrene is used to mean both α-methylstyrene and styrene. In the colored liquid (dye dispersion), the dispersant preferably contains at least one dispersant selected from the group consisting of a styrene-(meth)acrylic copolymer, a formalin condensate of an aromatic sulfonic acid or a salt thereof, a polyoxyethylene arylphenyl ether, a polyoxyethylene phenyl ether sulfate, and a polyoxyethylene naphthyl ether. The content of the dispersant in the colored liquid (dye dispersion) is usually 1 to 36%, preferably 1 to 30%, more preferably 1 to 20%, and even more preferably 1 to 15%.

Specific examples of the dispersant include Joncryl ^R™ 52J, 57J, 60J, 63J, 70J, JDX-6180, HPD-196, HPD96J, PDX-6137A, 6610, JDX-6500, JDX-6639, PDX-6102B, PDX-6124, 67, 678, 680, 682, 683, and 690 (manufactured by BASF), but are not limited thereto. In this specification, the superscript R™ denotes a registered trademark.

The dispersant in the coloring liquid preferably has a weight-average molecular weight of 1,000 to 20,000, more preferably 2,000 to 19,000, and particularly preferably 5,000 to 17,000. The weight-average molecular weight of the dispersant (such as a styrene-(meth)acrylic copolymer) is measured by gel permeation chromatography (GPC). The acid value of the styrene-(meth)acrylic copolymer used as the dispersant is preferably 50 to 250 mgKOH/g, more preferably 100 to 250 mgKOH/g, and particularly preferably 150 to 250 mgKOH/g. If the acid value is too low, the solubility of the dispersant (resin) in water will be reduced, and dispersion stabilization will tend to be poor, especially when the colorant is a dispersible dye. On the other hand, if the acid value is too high, the affinity with aqueous media will be strong, which will tend to cause bleeding in the printed image, which is undesirable. The acid value of the dispersant (resin) represents the number of milligrams of KOH required to neutralize 1 g of the dispersant (resin), and is measured in accordance with JIS-K 3054. Furthermore, 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.

Specific examples of styrene-(meth)acrylic copolymers, which are preferred dispersants in the above colored liquid, include Joncryl 67 (weight average molecular weight = 12,500, acid value = 213 mg KOH/g), 678 (weight average molecular weight = 8,500, acid value = 215 mg KOH/g), 682 (weight average molecular weight = 1,700, acid value = 230 mg KOH/g), 683 (weight average molecular weight = 4,900, acid value = 215 mg KOH/g), and 690 (weight average molecular weight = 16,500, acid value = 240 mg KOH/g), with Joncryl 678 being more preferred.

The colorant can be dispersed, for example, by the following method: A dispersant (such as a styrene-(meth)acrylic copolymer) is added to a water-soluble organic solvent, and the temperature is raised to 90-120°C to prepare a dispersant solution. An alkaline compound and water are then added, and the temperature is lowered to form an emulsified solution (emulsion or microemulsion). The resulting emulsion is then mixed with and dispersed into the colorant.

The formalin condensate of aromatic sulfonic acid or its salt is an anionic surfactant obtained by the condensation reaction of aromatic sulfonic acid and formalin. Examples of "salts thereof" include sodium salts, potassium salts, lithium salts, and the like. The formalin condensate of aromatic sulfonic acid or its salt is preferably a formalin condensate of aromatic sulfonic acid or its salt, or a mixture thereof (hereinafter, unless otherwise specified, the term "formalin condensate of sulfonic acid" also includes "its salt or a mixture thereof"). Examples include formalin condensates of creosote oil sulfonic acid, cresol sulfonic acid, phenol sulfonic acid, β-naphthalene sulfonic acid, β-naphthol sulfonic acid, β-naphthalene sulfonic acid and β-naphthol sulfonic acid, benzene sulfonic acid, cresol sulfonic acid, 2-naphthol-6-sulfonic acid, lignosulfonic acid, and methylnaphthalene sulfonic acid. Among these, formalin condensates of creosote oil sulfonic acid, β-naphthalene sulfonic acid, lignin sulfonic acid, and methylnaphthalene sulfonic acid are preferred. These are commercially available under various trade names. Examples include Demol N as a formalin condensate of β-naphthalene sulfonic acid, Demol C as a formalin condensate of creosote oil sulfonic acid, and Demol SN-B as a formalin condensate of special aromatic sulfonic acid (all manufactured by Kao Corporation). Examples of formalin condensates of creosote oil sulfonic acid include the Labelin W series, and examples of formalin condensates of methylnaphthalene sulfonic acid include the Labelin AN series (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). Among these, Demol N, the Labelin AN series, and the Labelin W series are preferred, with Demol N and Labelin W being more preferred, and Labelin W being even more preferred. Examples of lignin sulfonic acids include Vanilex N, Vanilex RN, Vanilex G, and Pearlex DP (all manufactured by Nippon Paper Industries Co., Ltd.). Of these, Vanilex RN, Vanilex N, and Vanilex G are preferred.

Examples of the polyoxyethylene aryl phenyl ether include styryl phenol compounds such as polyoxyethylene styryl phenyl ether, polyoxyethylene distyryl phenyl ether, polyoxyethylene tristyryl phenyl ether, and polyoxyethylene tetrastyryl phenyl ether; benzyl phenol compounds such as polyoxyethylene benzyl phenyl ether, polyoxyethylene dibenzyl phenyl ether, and polyoxyethylene tribenzyl phenyl ether; cumyl phenol compounds such as polyoxyethylene cumyl phenyl ether; polyoxyethylene naphthyl phenyl ether, polyoxyethylene biphenyl ether, and polyoxyethylene phenoxy phenyl ether. The number of repeating polyoxyethylene groups in the polyoxyethylene aryl phenyl ether is preferably 1 to 30, more preferably 15 to 30. A repeating number of 1 or more tends to provide excellent compatibility with aqueous solvents, etc. Furthermore, a repeating number of 30 or less tends to prevent excessively high viscosity. Among polyoxyethylene aryl phenyl ethers, polyoxyethylene styryl phenyl ether is preferred. Commercially available polyoxyethylene styryl phenyl ethers include, for example, Paionin D-6112, Paionin D-6115, Paionin D-6120, Paionin D-6131, Paionin D-6512, Takesurf D-6413, DTD-51, Paionin D-6112, and Paionin D-6320 (all manufactured by Takemoto Oil & Fat Co., Ltd.); TS-1500, TS-2000, TS-2600, and SM-174N (all manufactured by Toho Chemical Industry Co., Ltd.); and Emulgen A-60, Emulgen A-90, and Emulgen A-500 (all manufactured by Kao Corporation).

The polyoxyethylene aryl phenyl ether sulfates include the above-mentioned polyoxyethylene styryl phenyl ether sulfates. Of the above-mentioned polyoxyethylene aryl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfate is preferred. Commercially available polyoxyethylene styryl phenyl ether sulfates include, for example, SM-57 and SM-210 (both manufactured by Toho Chemical Industry Co., Ltd.).

Examples of commercially available polyoxyethylene naphthyl ethers include the Noigen EN series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and Paionin D-7240 (manufactured by Takemoto Yushi Co., Ltd.).

In one preferred embodiment, the polyoxyethylene aryl phenyl ether is polyoxyethylene styryl phenyl ether and/or the polyoxyethylene aryl phenyl ether sulfate is polyoxyethylene styryl phenyl ether sulfate.

In addition to the dispersants described above, the coloring liquid may further contain a conventionally known nonionic dispersant. Examples of nonionic dispersants include alkylene oxide adducts of cholestanols, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, oxyethyleneoxypropylene block polymers, and substituted derivatives thereof. Preferred alkylene oxide adducts of cholestanols are C2-C4 alkylene oxide adducts of cholestanols, with ethylene oxide adducts being more preferred. In this specification, the term "cholestanols" encompasses both "cholestanol" and "hydrogenated cholestanol." For example, ethylene oxide adducts of cholestanols include the ethylene oxide adduct of cholestanol and the ethylene oxide adduct of hydrogenated cholestanol. The amount of alkylene oxide (preferably C2-C4 alkylene oxide, more preferably ethylene oxide) added per mole of cholestanols is preferably about 10-50 moles, and the HLB is preferably about 13-20.

The above dispersants may be used alone or in combination of two or more.

The above coloring liquid may further contain water.

The water used is preferably ion-exchanged water, distilled water, or other water with few impurities. The colored liquid can also be subjected to microfiltration using a membrane filter or similar. When using the colored liquid as an inkjet printing ink, microfiltration is preferred to prevent nozzle clogging. The pore size of the filter used for microfiltration is typically 1 μm to 0.1 μm, and preferably 0.8 μm to 0.1 μm.

The coloring liquid may further contain a phytosterol compound.
The phytosterol-based compound refers to a compound having a phytosterol skeleton in the molecule, and examples thereof include alkylene oxide adducts of phytosterols. As alkylene oxide adducts of phytosterols, C2-C4 alkylene oxide adducts of phytosterols are preferred, and ethylene oxide adducts are more preferred. In this specification, the term "phytosterols" is used to include both "phytosterol" and "hydrogenated phytosterol." For example, ethylene oxide adducts of phytosterols include ethylene oxide adducts of phytosterol and ethylene oxide adducts of hydrogenated phytosterol. The amount of alkylene oxide (preferably C2-C4 alkylene oxide, more preferably ethylene oxide) added per mole of phytosterol is preferably about 10 to 50 moles, and the HLB is preferably about 13 to 20. Commercially available alkylene oxide adducts of phytosterols include, for example, NIKKOL BPS-20 and NIKKOL BPS-30 (both manufactured by Nikko Chemicals Co., Ltd., ethylene oxide adducts of phytosterols), and NIKKOL BPSH-25 (also manufactured by Nikko Chemicals Co., Ltd., ethylene oxide adduct of hydrogenated phytosterols). Commercially available alkylene oxide adducts of cholestanols include, for example, NIKKOL DHC-30 (manufactured by Nikko Chemicals Co., Ltd., ethylene oxide adduct of cholestanol), with NIKKOL BPS-30 being preferred.

The above coloring liquid may further contain additives.

Examples of the above additives include surfactants, water-soluble organic solvents, preservatives, pH adjusters, chelating agents, rust inhibitors, water-soluble UV absorbers, water-soluble polymer compounds, viscosity adjusters, dye dissolving agents, anti-fading agents, antioxidants, etc.

Examples of the surfactant include known surfactants such as anionic, cationic, amphoteric, nonionic, silicone, and fluorine-based surfactants. Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acylamino acids and their salts, N-acylmethyl taurines, alkyl sulfates, polyoxyalkyl ether sulfates, alkyl sulfates, polyoxyethylene alkyl ether phosphates, rosin acid soaps, castor oil sulfates, lauryl alcohol sulfates, alkylphenol phosphates, alkyl phosphates, alkylaryl sulfonates, diethyl sulfosuccinates, diethylhexyl sulfosuccinates, and dioctyl sulfosuccinates. Specific examples of commercially available surfactants include Hitenol LA-10, LA-12, and LA-16, Neohitenol ECL-30S, and ECL-45, all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. Examples of cationic surfactants include 2-vinylpyridine derivatives, poly(4-vinylpyridine) derivatives, etc. Examples of amphoteric surfactants include lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, polyoctyl polyaminoethyl glycine, and imidazoline derivatives. Examples of nonionic surfactants include 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-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, and 3,5-dimethyl-1-hexyne-3-ol; Surfynol 104, 105, 82, and 465 (trade names) and Olfine STG (trade names) manufactured by Nissin Chemical Co., Ltd.; and polyglycol ether-based surfactants (for example, Tergitol manufactured by SIGMA-ALDRICH). 15-S-7, etc.); and the like.

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 manufactured by BYK-Chemie. Examples of fluorine-based 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 on the side chain. 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.

The water-soluble organic solvent is not particularly limited, but examples include glycol-based solvents, polyhydric alcohols, and pyrrolidones. Examples of glycol-based solvents include glycerin, polyglycerin (#310, #750, #800), diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, undecaglycerin, dodecaglycerin, tridecaglycerin, and tetradecaglycerin, as well as mixtures thereof. Examples of polyhydric alcohols include C2-C6 polyhydric alcohols having two to three alcoholic hydroxyl groups, di- or tri-C2-C3 alkylene glycols, or poly-C2-C3 alkylene glycols with four or more repeating units and a molecular weight of approximately 20,000 or less, preferably liquid polyalkylene glycols. Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, thiodiglycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, glycerin, trimethylolpropane, 1,3-pentanediol, 1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methoxy-1-butanol, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether. Examples of pyrrolidones include 2-pyrrolidone, N-methyl-2-pyrrolidone, and 1-(2-hydroxyethyl)-2-pyrrolidone. The water-soluble organic solvent preferably contains at least either glycerin or diglycerin. For convenience, compounds that dissolve in water and act as humectants are also considered to be included in the water-soluble organic solvent in the present invention, such as urea, ethylene urea, and sugars. Considering storage stability, when the water-insoluble colorant is a disperse dye or an oil-soluble dye, a solvent with low solubility is preferred. Among these, it is particularly preferred to use glycerin in combination with a solvent other than glycerin (preferably a polyhydric alcohol other than glycerin). The total content of the water-soluble organic solvent in the total mass of the coloring liquid is typically 5 to 50%, and preferably 10 to 40%.

Examples of the preservative include organic sulfur compounds, organic nitrogen sulfur compounds, organic halogen compounds, haloarylsulfone compounds, iodopropargyl compounds, N-haloalkylthio compounds, nitrile compounds, pyridine compounds, 8-oxyquinolines, benzothiazole compounds, isothiazolinone compounds, dithiols, pyridine oxide compounds, nitropropane compounds, organic tin compounds, phenol compounds, quaternary ammonium salt compounds, triazine compounds, thiazine compounds, anilides, adamantane compounds, dithiocarbamates, brominated indanone compounds, benzyl bromoacetate compounds, and inorganic salt compounds. Specific examples of organic halogen compounds include sodium pentachlorophenol, specific examples of pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide, and specific examples of isothiazoline 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, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Specific examples of other preservatives (antiseptic and antifungal agents) include sodium acetate anhydride, sodium sorbate, or sodium benzoate, and products of Lonza, such as Proxel ^R™ GXL(S) and Proxel ^R™ XL-2(S).

Any substance can be used as the pH adjuster as long as it can control the pH of the solution to a range of approximately 5 to 11 without adversely affecting the coloring liquid being adjusted. 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 (aqueous ammonia); 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, with triethanolamine being preferred.

Specific examples of the above chelating reagents include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracildiacetate, etc.

Examples of the above-mentioned rust inhibitors include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

Examples of the above-mentioned water-soluble ultraviolet absorbers include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

Examples of the above-mentioned water-soluble polymer compounds include polyvinyl alcohol, cellulose derivatives, polyamines, or polyimines.

In addition to water-soluble organic solvents, the viscosity adjuster may also include water-soluble polymer compounds, such as polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

Examples of the dye dissolving agents include urea, ε-caprolactam, ethylene carbonate, etc.

The above-mentioned anti-fading agents are used to improve the storage stability of images. Various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Metal complex anti-fading agents include nickel complexes and zinc complexes.

The antioxidant may be, for example, a variety of organic and metal complex antioxidants. Examples of organic antioxidants include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles.

In the above coloring liquid, it is preferable that the above additive contains at least one selected from the group consisting of a water-soluble organic solvent, a preservative, and a pH adjuster.

The above coloring liquid may further contain a resin emulsion.

The above-mentioned resin emulsions include, for example, emulsions formed from acrylic resin, epoxy resin, urethane resin, polyether resin, polyamide resin, unsaturated polyester resin, phenolic resin, silicone resin, fluororesin, polyvinyl resin (e.g., polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, etc.), alkyd resin, polyester resin, or amino material (melamine resin, urea resin, urea resin, melamine formaldehyde resin, etc.). These emulsions may also be composed of two or more resins. They may also be composite resins in which two or more resins form a core/shell structure. Of these resin emulsions, urethane resin is preferred for use in the above-mentioned coloring liquid.

Many of the above urethane resins are sold in the form of latex (emulsion), most of which are emulsions with a solids content of 30-60%. Specific examples include Permarin UA-150, 200, 310, 368, 3945, and U-coat UX-320 (all manufactured by Sanyo Chemical Industry Co., Ltd.), Hydran WLS-201, 210, and HW-312B latex (all manufactured by DIC Corporation), and Superflex 150, 170, and 470 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). Among these, examples of polycarbonate-based urethane resins include Permarin UA-310, 3945, and U-coat UX-320. Among these, examples of polyether-based urethane resins include Permarin UA-150, 200, and U-coat UX-340. These urethane resins can be used alone or in combination.

The above urethane resin emulsion preferably has an SP value (solubility parameter) of 8 to 24, more preferably 8 to 17, and particularly preferably 8 to 11. Furthermore, if the resin in the urethane resin emulsion has acidic groups, and these acidic groups have been neutralized to prepare the emulsion, the SP value of the resin before neutralization is used.

If the above urethane resin emulsion has acidic groups such as carboxylic acid, sulfonic acid, or hydroxyl groups, these acidic groups may be converted into alkali salts. Alkali salts can be produced, for example, by the following method. One example is to add a urethane resin emulsion containing acidic groups to water and stir it to prepare an aqueous solution, then add an alkaline compound to the aqueous solution to prepare a liquid with a pH adjusted to 6.0-12.0.

Examples of the alkaline compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide; and triethylamine. These alkaline compounds may be used alone or in combination of two or more.

The coloring liquid can be prepared, for example, by mixing the components. There are no particular restrictions on the order in which the components are mixed.

The above coloring liquid may be used as ink as is, or it may be used as ink by adding or increasing the amount of water, dispersants, surfactants, pH adjusters, additives, etc. to the above coloring liquid.

Methods for dispersing the coloring liquid include known methods, such as stirring and mixing the components that make up the coloring liquid using a sand mill (bead mill), roll mill, ball mill, paint shaker, ultrasonic disperser, or high-pressure emulsifier. For example, when using a sand mill, first charge the components and beads as a dispersion medium into the sand mill. Examples of beads that can be used include glass beads, zirconia beads, and the like, with particle sizes of 0.01 to 1 mm. The amount of beads used is preferably 2 to 6 parts by weight per 1 part by weight of the material to be dispersed. The sand mill is then operated to perform the dispersion process. The preferred dispersion conditions are approximately 1,000 to 2,000 rpm and 1 to 20 hours. After the dispersion process, the beads are removed by filtration or other means to obtain the dispersed coloring liquid.

The above colorants may be mixed and dispersed during dispersion to obtain a colored liquid, or liquids in which water-insoluble colorants are each dispersed may be mixed.

The present invention also includes a dye bath for immersion dyeing containing the above coloring liquid.

The prepared colored liquid may be subjected to microfiltration using a membrane filter or the like. When using the colored liquid as an ink for inkjet textile printing, it is particularly preferable to perform microfiltration to prevent nozzle clogging. The pore size of the filter used for microfiltration is usually 0.1 to 1 μm, and preferably 0.1 to 0.8 μm.

In terms of high-speed ejection response, the above-mentioned inkjet textile printing ink (hereinafter sometimes abbreviated to ink) preferably has a viscosity at 25°C of approximately 3 to 20 mPa·s when measured using an E-type viscometer. Furthermore, the surface tension, when measured using the plate method, preferably falls within the range of 20 to 45 mN/m. It is preferable to adjust these values appropriately, taking into account the ejection volume, response speed, and ink droplet flight characteristics of the printer being used.

The present invention also includes a coloring liquid set containing the above coloring liquid and another coloring liquid, and an ink set containing an ink when the above coloring liquid is used as an ink for inkjet textile printing and another ink when the above other coloring liquid is used as an ink for inkjet textile printing.
The other inks refer to inks having a different composition and hue from the above inks, and examples thereof include, but are not limited to, yellow ink, magenta ink, black ink, orange ink, violet ink, turquoise ink, blue ink, fluorescent pink ink, and fluorescent yellow ink. Furthermore, low-concentration inks or high-concentration inks in which the total concentration of the colorant in the ink is changed may be used in comparison with the above inks or the other inks. Examples of low-concentration inks include light yellow ink, light magenta ink, light cyan ink, and light black ink. When forming the ink set, for example, each color ink may contain one type of colorant, or two or more types may be used in combination. The colorants contained in each ink constituting the ink set may be known colorants and are not particularly limited.

Examples of colorants that may be contained in the other inks include disperse dyes and oil-soluble dyes. Specific examples of disperse dyes include C.I. Disperse Yellow 3, 4, 5, 7, 9, 13, 24, 30, 33, 34, 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, 12 2, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184, 186, 192, 198, 199, 201, 202, 204, 210, 211, 215, 216, 218, 224, 231, 232, 241, etc.; C. I. C.I. Disperse Orange 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 26, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 47, 48, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139, 142, etc.; C.I. Disperse Red 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 1 54, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 22 4, 225, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 289, 298, 302, 303, 310, 311, 312, 320, 324, 328, 343, 362, 364, etc.; C. I. C.I. Disperse Violet 1, 4, 8, 17, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, 77, etc.; C.I. Disperse Green 6:1, 9, etc.; C.I. Disperse Brown 1, 2, 4, 9, 13, 19, 26, 27, etc.; C.I. Disperse Blue 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 79, 81, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143, 146, 148, 149, 153, 154, 1 58, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 267, 268, 270, 284, 285, 287, 288, 291, 293, 295, 297, 301, 315, 330, 332, 333, 334, 343, 359, 360, etc.; C.I. Disperse Black 1, 3, 10, 24, etc.;

Specific examples of the above oil-soluble dyes include C.I. Solvent Yellow 2, 6, 14, 16, 21, 25, 29, 30, 33, 51, 56, 77, 80, 82, 88, 89, 93, 116, 150, 163, 179, etc.; C.I. Solvent Orange 1, 2, 14, 45, 60, etc.; C.I. Solvent Red 1, 3, 7, 8, 9, 18, 19, 23, 24, 25, 27, 49, 100, 109, 121, 122, 125, 127, 130, 132, 135, 218, 225, 230, etc.; C.I. Solvent Violet 13, 31, etc.; C.I. Solvent Green 3, etc.; Solvent Brown 3, 5, etc.: C.I. Solvent Blue 2, 11, 14, 24, 25, 35, 36, 38, 48, 55, 59, 63, 67, 68, 70, 73, 83, 105, 111, 132, etc.: C.I. Solvent Black 3, 5, 7, 23, 27, 28, 29, 34, etc.: and the like.

The colorants that may be contained in the other inks mentioned above may be used alone or in combination with multiple types.

The present invention also includes recorded materials obtained by using (e.g., applying) the above-mentioned coloring liquid or the above-mentioned coloring liquid set to recording media.

The recording medium is not particularly limited as long as it can be used to record using the coloring liquid or ink containing the coloring liquid, but examples include paper and fabric, with fabric, particularly hydrophobic fiber, being preferred.

Specific examples of the hydrophobic fibers include polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, polyamide fibers, and blended fibers using two or more of these fibers. Blends of these with regenerated fibers such as rayon, and natural fibers such as cotton, silk, and wool are also included in the hydrophobic fiber category in this specification. Some of these hydrophobic fibers are known to have an ink-receiving layer (bleed-preventing layer), and such hydrophobic fibers are also included. Methods for forming an ink-receiving layer are well-known, and fibers with ink-receiving layers are commercially available. The material and structure of the ink-receiving layer are not particularly limited, and can be used as appropriate depending on the purpose.

The above coloring liquid can be used in a variety of fields, but is suitable for use as a water-based writing ink, water-based printing ink, information recording ink, textile printing, etc., and is particularly preferred for use as an inkjet textile printing ink.

The present invention also includes a hydrophobic fiber printing method that includes a printing step in which droplets of the coloring liquid or the coloring liquid set are deposited on an intermediate recording medium to obtain a recorded image, and a transfer step in which the recorded image is transferred to the hydrophobic fiber by contacting the hydrophobic fiber with the surface of the intermediate recording medium on which the droplets of the coloring liquid or the coloring liquid set have been deposited and then heat-treating the hydrophobic fiber. The present invention also includes an intermediate recording medium on which droplets of the coloring liquid or the coloring liquid set have been deposited.

The above-mentioned hydrophobic fiber printing methods can be broadly divided into two types. The first method, known as direct printing or direct textile printing, is a method for printing hydrophobic fibers that includes at least three steps: Step A, in which droplets of the coloring liquid or the coloring liquid set are applied to the hydrophobic fiber using an inkjet printer to form image information such as letters and patterns on the hydrophobic fiber; Step B, in which the sublimable dye (water-insoluble colorant) in the droplets of the coloring liquid or the coloring liquid set applied in Step A is fixed to the fiber by heat; and Step C, in which any unfixed sublimable dye remaining in the fiber is washed away. Step B is generally performed by known methods such as steaming or baking. Examples of steaming include a method of treating hydrophobic fibers with a sublimation dye (also called wet heat fixation) using a high-temperature steamer, typically at 170 to 180°C, typically for about 10 minutes; and a method of treating hydrophobic fibers with a high-pressure steamer, typically at 120 to 130°C, typically for about 20 minutes. Examples of baking (thermosol) include a method of treating hydrophobic fibers with a sublimation dye (also called dry heat fixation) using a high-temperature steamer, typically at 190 to 210°C, typically for about 60 to 120 seconds. Step C is a step of washing the obtained fibers with warm water and, if necessary, water. The warm water or water used for washing may contain a surfactant. The washed fibers are preferably dried, typically at 50 to 120°C, for 5 to 30 minutes. The second method is known as sublimation transfer printing or sublimation transfer textile printing. This method involves depositing droplets of the coloring liquid or the coloring liquid set on an intermediate recording medium using an inkjet printer to form a recorded image, such as letters or a design. Then, the surface of the intermediate recording medium onto which the droplets of the coloring liquid or the coloring liquid set have been deposited is brought into contact with a hydrophobic fiber, followed by heat treatment, thereby transferring the image, such as the letters or design, recorded on the intermediate recording medium to the hydrophobic fiber. The intermediate recording medium is preferably one in which the sublimable dye (water-insoluble colorant) in the coloring liquid or the coloring liquid set deposited on the intermediate recording medium does not aggregate on its surface and does not interfere with the sublimation of the dye when the recorded image is transferred to the hydrophobic fiber. An example of such an intermediate recording medium is paper having a dye dispersion-receiving layer formed on its surface using inorganic fine particles such as silica. Paper specifically designed for inkjet printing can be used. The heat treatment carried out when transferring the recorded image from the intermediate recording medium to the hydrophobic fiber is usually a dry heat treatment at about 190 to 200°C.

In the above-mentioned dip dyeing method, hydrophobic fibers are immersed in the coloring solution of the present invention and dyed under pressure at a temperature of preferably 105°C or higher, more preferably 110 to 140°C, for preferably 30 minutes to 1 hour. Dyeing at 120 to 130°C is particularly preferred for 30 to 45 minutes. Dyeing can also be carried out in the presence of a carrier such as o-phenylphenol or trichlorobenzene, for example, in boiling water. Alternatively, dyeing can also be carried out using the so-called thermosol method, in which the coloring solution of the present invention is padded onto hydrophobic fibers and then dry-heat treated at 150 to 230°C.

The above-mentioned textile printing method may further include a fiber pretreatment step to prevent bleeding and other problems. This pretreatment step includes applying an aqueous solution containing at least one type of sizing agent, an alkaline substance, an anti-reducing agent, and a hydrotropic agent to the fibers before applying the coloring liquid or ink containing the coloring liquid. The pretreatment step preferably involves impregnating the fibers with an aqueous solution of a pretreatment agent containing a sizing agent, an alkaline substance, an anti-reducing agent, and a hydrotropic agent. Examples of sizing agents include natural gums such as guar and locust bean, starches, sodium alginate, seaweed such as funori, plant skins such as pectic acid, cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose, modified starches such as carboxymethyl starch, and synthetic glues such as polyvinyl alcohol and polyacrylic esters. Sodium alginate is preferred.

Examples of the alkaline substance include alkali metal salts of inorganic or organic acids, alkaline earth metal salts, and compounds that liberate alkali when heated. Preferred are inorganic or organic alkali metal hydroxides and alkali metal salts, including sodium and potassium compounds. 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. Sodium bicarbonate is preferred. The reduction inhibitor is preferably sodium meta-nitrobenzenesulfonate. Examples of the hydrotropic agent include urea, dimethyl urea, and other ureas, with urea being preferred. The sizing agent, alkaline substance, reduction inhibitor, and hydrotropic agent may each be a single compound or multiple compounds may be used in combination. The mixing ratio of each pretreatment agent in the total mass of the pretreatment liquid is, for example, 0.5 to 5% by mass of sizing agent, 0.5 to 5% by mass of alkaline substance (sodium bicarbonate, etc.), 0 to 5% by mass of anti-reducing agent (sodium meta-nitrobenzenesulfonate, etc.), 1 to 20% by mass of hydrotropic agent (urea, etc.), and the remainder is water. The pretreatment agent can be applied to cellulosic fibers by, for example, a padding method. The squeezing rate of padding is preferably about 40 to 90%, and more preferably about 60 to 80%.

The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means parts by mass and "%" means % by mass. Note that the inks in each example are all included in the coloring liquid described above.

The compounds represented by the following formulas (B-1) and (C-1) were prepared by reference to the methods described in JP-B-5-065358 and the non-patent document Zhurnal Organicheskoi Khimii, Volume 18, Issue 7, Pages 1539-49.

Preparation Example 1: Preparation of Joncryl 678 emulsion
Joncryl 678 (manufactured by BASF) (20 parts) was added to a mixture of 25% sodium hydroxide (6 parts), ion-exchanged water (54 parts), and propylene glycol (20 parts), and the mixture was heated to 90 to 120°C and stirred for 5 hours to obtain an emulsion of Joncryl 678.

Preparation Example 2: Preparation of aqueous dispersion 1
As a colorant, commercially available C.I. Disperse Blue 359 (10 parts), Labelin W-40 (creosote oil sodium sulfonate formalin polycondensate aqueous solution, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) (15 parts), NIKKOL BPS-30 (phytosterol ethylene oxide adduct, manufactured by Nikko Chemicals Co., Ltd.) (0.8 parts), Surfynol 104PG50 (Surfynol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted to a 50% concentration with propylene glycol) (0.2 parts), Proxel GXL (S) (manufactured by Lonza) (0.1 parts), and ion-exchanged water (73.9 parts) were added to a mixture, and 0.2 mm diameter glass beads were added, followed by dispersion treatment for about 15 hours under cooling in a sand mill. The resulting liquid was filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size: 0.5 μm) to obtain aqueous dispersion 1.

Preparation Example 3: Preparation of aqueous dispersion 2
An aqueous dispersion 2 was obtained in the same manner as in Preparation Example 2, except that the colorant was changed to the compound represented by formula (B-1) (10 parts).

Preparation Example 4: Preparation of aqueous dispersion 3
Aqueous dispersion 3 was obtained in the same manner as in Preparation Example 2, except that the colorant was changed to the compound represented by formula (C-1) (10 parts).

Preparation Example 5: Preparation of aqueous dispersion 4
To a mixture of C.I. Disperse Blue 359 (10 parts) as a colorant, the above-mentioned Joncryl 678 emulsion (30 parts), Surfynol 104PG50 (Surfynol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted to a 50% concentration with propylene glycol) (0.2 parts), Proxel GXL(S) (manufactured by Lonza) (0.1 parts), and ion-exchanged water (59.7 parts), 0.2 mm diameter glass beads were added, and the mixture was dispersed in a sand mill under cooling for about 15 hours. The resulting liquid was filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC Co., Ltd., filter pore size: 0.5 μm) to obtain aqueous dispersion 4.

Preparation Example 6: Preparation of Aqueous Dispersion 5
Aqueous dispersion 5 was obtained in the same manner as in Preparation Example 5, except that the colorant was changed to the compound represented by formula (B-1) (10 parts).

Preparation Example 7: Preparation of Aqueous Dispersion 6
A mixture of C.I. Disperse Blue 359 (10 parts) as a colorant, SM-57 (manufactured by Toho Chemical Industry Co., Ltd., polyoxyethylene styryl phenyl ether sulfate-based dispersant) (10 parts), Surfynol 104PG50 (Surfynol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted to a 50% concentration with propylene glycol) (0.2 parts), Proxel GXL(S) (manufactured by Lonza) (0.1 parts), and ion-exchanged water (79.7 parts) was added with 0.2 mm diameter glass beads, and the mixture was dispersed in a sand mill under cooling for about 15 hours. The resulting liquid was filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC Co., Ltd., filter pore size: 0.5 μm) to obtain aqueous dispersion 6.

Preparation Example 8: Preparation of aqueous dispersion 7
Aqueous dispersion 7 was obtained in the same manner as in Preparation Example 7, except that the colorant was changed to the compound represented by formula (B-1) (10 parts).

[Preparation Example 9: Preparation of Examples and Comparative Examples]
The aqueous dispersions 1 to 7 obtained above were mixed with the components shown in Table 1 below, stirred for 30 minutes, and then filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size: 0.5 μm) to prepare inks for Examples 1 to 11 and Comparative Examples 1 and 2. In the table, the numerical value for each component indicates the number of parts added.

The abbreviations in Table 1 below represent the following:
Proxel GXL: Proxyl GXL (S), a preservative manufactured by Lonza Surfynol 465: a nonionic surfactant manufactured by Nissin Chemical Industry Co., Ltd. TEA-80: an 80% aqueous solution of triethanolamine X/Y: a value calculated by the relational expression X, the total mass of (a) above, divided by Y, the total mass of (b) above

The following evaluation tests were conducted using the ink prepared as described above. The evaluation results are shown in Table 1. "N/A" in Table 1 indicates not applicable.

[Intermediate recording medium printed with ink and sublimation transfer printing using the same]
Each of the prepared inks was filled into an inkjet printer (manufactured by EPSON Corporation, product name PX-504A), and TRANSJET EcoII 8385 (95 g/m ² ) was used as the intermediate recording medium to print gradation images in 5% duty increments from 0% to 100% duty, to obtain intermediate recording media. The colored liquid-attached surface of each of the obtained intermediate recording media was superimposed on a polyester cloth (Teijin Tropical), and then heat-treated at 200°C for 60 seconds using a tabletop automatic flat press (manufactured by Asahi Textile Machinery Co., Ltd.: AF-65TEN), to obtain dyed products dyed by the sublimation transfer dyeing method. The obtained dyed products were evaluated as follows.

[Saturation evaluation]
The dyed portion of each of the obtained dyed products was measured using a spectrophotometer "Ci62 (manufactured by X-rite)" to measure the L ^* value and C ^* value of each dyed product. The color measurement was performed under conditions of a D65 light source, a viewing angle of 2°, and status T. The saturation (C ^* value) was evaluated in the L ^* value range of 41.5 to 43.5. The higher the C ^* value, the higher the saturation and the wider the color gamut of the hue that can be expressed.
[Evaluation criteria]
A: Over 60.
B: Over 59 and under 60.
C: 58 or above, but under 59.
D: Under 58.

[Evaluation of color development]
The 100% duty dyed portion of each of the obtained dyed products was measured using a spectrophotometer "Ci62 (manufactured by X-rite)" to measure the density of each dyed product. Colorimetry was performed under conditions of a D65 light source, a viewing angle of 2°, and status T. The reflectance R of each dyed product at 400 to 700 nm was measured, and the K/S value was calculated using the Kubelka-Munk formula: K/S = (1 - R) ² /2R. Furthermore, the sigma K/S value, which is the sum of the K/S values at each wavelength, was calculated. A larger sigma K/S value indicates higher color density and higher quality. Based on the calculated sigma K/S value, evaluation was performed according to the following evaluation criteria.
[Evaluation criteria]
A: 210 or more.
B: 200 or more but less than 210.
C: 190 or more but less than 200.
D: Less than 190.

[Evaluation of ejection stability]
Each ink was filled into an inkjet printer, and it was confirmed that there were no clogged nozzles and that printing was possible from all nozzles. The cartridges containing the ink were removed and left in an environment of 60°C for 14 days. These were then filled into the inkjet printer again, and cleaning was performed twice and 100 sheets were printed, printing a check pattern. The number of white spots in the check pattern was counted. The greater the number of white spots, the worse the storage stability of the ink and the worse the ejection stability during printing. Evaluation was performed according to the following evaluation criteria.
[Evaluation criteria]
A: Less than 2 pieces.
B: 2 or more, but less than 4.
C: 4 or more but less than 6.
D: 6 or more.

As is clear from the evaluation results in Table 1, the inks prepared in Examples 1 to 12 have higher saturation, excellent ejection stability, and high color development compared to the inks in Comparative Examples 1 to 4.

The coloring liquid of the present invention has high color development and saturation, and has good ejection stability, making it possible to produce high-quality cyan to blue dyed products.It also maintains the printability required for various textile printing inks, particularly inkjet textile printing inks, making it extremely useful as a cyan ink for sublimation transfer inkjet textile printing.

Claims (12)

The ink composition contains at least a water-insoluble colorant,
(a) Compound A, in which any one of the substituents R ¹ to R ⁶ in the following formula (1) is a cyano group and the other five are hydrogen atoms; and
(b) A colored liquid containing at least one compound selected from the group consisting of: a compound B in which at least two of the substituents R ¹ to R ⁶ in the following formula (1) are cyano groups and all of the substituents other than the cyano groups are hydrogen atoms; and a compound C in which the substituents R ¹ to R ⁶ in the following formula (1) are all hydrogen atoms, wherein the total mass X of (a) above and the total mass Y of (b) above satisfy the relationship 10≦ X/Y ≦490 .
2. The colored liquid according to claim 1, wherein the compound A is a compound represented by the formula (1) in which the substituent R ¹ is a cyano group. 3. The colored liquid according to claim 1, wherein the compound B is a compound represented by the formula (1) in which the substituents R ¹ and R ² are each a cyano group. The coloring liquid according to any one of claims 1 to 3, further comprising a dispersant. The coloring liquid according to claim 4, wherein the dispersant contains at least one selected from the group consisting of a styrene-(meth)acrylic copolymer, a formalin condensate of an aromatic sulfonic acid or a salt thereof, polyoxyethylene arylphenyl ether, polyoxyethylene arylphenyl ether sulfate, and polyoxyethylene naphthyl ether. The coloring solution according to claim 5, wherein the formalin condensate of an aromatic sulfonic acid or its salt includes a formalin condensate of creosote oil sulfonic acid or its salt. The coloring liquid according to claim 5 or 6, wherein the polyoxyethylene aryl phenyl ether is polyoxyethylene styryl phenyl ether, and/or the polyoxyethylene aryl phenyl ether sulfate is polyoxyethylene styryl phenyl ether sulfate. The coloring liquid according to any one of claims 1 to 7, further comprising a phytosterol compound. A coloring liquid set comprising the coloring liquid according to any one of claims 1 to 8 and another coloring liquid. A recorded matter obtained by applying the coloring liquid described in any one of claims 1 to 8 or the coloring liquid set described in claim 9 to a recording medium. The recorded matter described in claim 10, wherein the recording medium is a hydrophobic fiber. A method for printing hydrophobic fibers, comprising: a printing step in which droplets of the coloring liquid described in any one of claims 1 to 8 or the coloring liquid set described in claim 9 are deposited on an intermediate recording medium to obtain a recorded image; and a transfer step in which the recorded image is transferred to the hydrophobic fiber by contacting the hydrophobic fiber with the surface of the intermediate recording medium on which the droplets of the coloring liquid or the coloring liquid set have been deposited and then heat-treating the hydrophobic fiber.