WO2022075025A1 - Coloring fluid, coloring fluid set, recorded matter, and method for printing hydrophobic fiber - Google Patents

Abstract

The present invention addresses the problem of providing a coloring fluid having a wide expression range of hues in the cyan-blue region, and also having excellent coloring properties and discharge stability. A means for resolving this problem includes at least a non-water-soluble coloring agent, the non-water-soluble coloring agent including at least a compound selected from the group comprising: (a) a compound A in which any one of the substituents R1 to R6 in expression (1) is a cyano group, and the other five are hydrogen atoms; (b) a compound B in which any two of the substituents R1 to R6 in expression (1) are cyano groups, and all of the substituents other than the cyano groups are hydrogen atoms; and a compound C in which all of the substituents R1 to R6 in expression (1) are hydrogen atoms, the total mass X of (a) and the total mass Y of (b) satisfying the expression X/Y ≥ 7.4.

Description

Printing method for colored liquids, colored liquid sets, recorded materials and hydrophobic fibers

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

In recent years, a recording method for plate-free printing by inkjet has been proposed, and inkjet printing is also performed for textile printing including cloth and the like. Compared to conventional printing methods such as screen printing, printing by inkjet printing has various features such as plate-free printing, resource saving, energy saving, and easy high-definition expression. There are advantages. Here, the hydrophobic fiber cloth such as polyester fiber is generally dyed with a coloring material insoluble in water. Therefore, as a water-based ink for printing hydrophobic fibers by an inkjet recording method, it is generally necessary to disperse a water-insoluble coloring material in water and use a dispersed ink having good performance such as dispersion stability. Inkjet printing methods for hydrophobic fibers typified by polyester fibers are roughly classified into the following two methods. A direct printing method in which the dye in the ink is dyed on the fibers by heat treatment such as high-temperature steaming after directly applying (printing) ink to the fibers, and applying ink (printing) to an intermediate recording medium (dedicated transfer paper, etc.). This is a sublimation transfer method in which the ink-applied surface of the intermediate recording medium and the hydrophobic fiber are overlapped with each other, and then the dye is transferred from the intermediate recording medium to the fiber side by heat.

Of the above, the sublimation transfer method is mainly used for printing of banners and the like, and an easy sublimation type dye having excellent transfer suitability to polyester by heat treatment is used in the ink. As a processing process,
(1) Printing process: A process of applying dye ink to an intermediate recording medium by an inkjet printer.
(2) Transfer step: A step of transferring and dyeing a dye from an intermediate recording medium into a fiber by heat treatment.
Since the transfer paper on the market can be widely used, the pretreatment of the fiber is not required and the cleaning step is omitted.

Ink ejection stability is one of the performance requirements for ink used in inkjet printing. In the inkjet recording method, it is necessary to eject ink as small droplets from a thin nozzle, and there is a demand for a coloring liquid that does not cause ejection defects even in continuous operation for a long time and can obtain a high-quality printed matter. .. In Patent Document 1, a water-soluble organic solvent as a moisturizing agent and a surfactant as a surface tension adjusting agent are used for a dye dispersion liquid in which a water-insoluble colorant selected from a dispersion dye and an oil-soluble dye is dispersed in water. , And other additives (pH adjusters, antiseptic and antifungal agents, antifoaming agents, etc.) are described to adjust the ink.

As the performance required for a water-insoluble colorant, it is necessary to have good sublimation property, high color development on hydrophobic fibers, and excellent fastness. Therefore, the dyes widely used in the market are limited, and the color reproduction range is similar to that of each company. Inkjet printer inks and paints are known to express colors by subtractive color mixing, and a four-color ink set that adds black to the "three primary colors" of cyan, magenta, and yellow is the basis. ..

As a colorant used for cyan ink in the sublimation transfer method, C.I. I. Disperse Blue 359 is known, and C.I. I. By using Disperse Blue 359, it is possible to obtain a good hue of blue with high saturation. However, there is a problem that the discharge stability of the coloring liquid is lowered when the colorant is used alone, and improvement of the discharge stability is required.

International Publication No. 2005/121263

However, by combining a colorant, it is possible to suppress recrystallization of the colorant in the ink, prevent nozzle blockage due to inkjet printing, and improve ejection stability. It causes deterioration of color development and saturation of the printed matter. Therefore, C.I. I. It was difficult to obtain a coloring liquid having the same color-developing property as Disperse Blue 359, having a wider color gamut than the colorant, and having excellent ejection stability.

An object of the present invention is to provide a coloring liquid having a wide hue expression range in the cyan to blue region and excellent in color development and ejection stability.

As a result of diligent studies, the present inventors have found that the water-insoluble colorant contains at least a water-insoluble colorant.
(A) Compound A, in which any one of the substituents ^R1 to R6 in the following formula ( ¹ ) is a cyano group and the other five are hydrogen atoms.
(B) Compound B in which at least ^two of the substituents ^R1 to R6 in the following formula (1) are cyano groups and all the substituents other than the cyano group are hydrogen atoms, in the following formula (1). The total mass X of the above (a) and the total mass Y of the above (b) include at least one compound selected from the group consisting of the compound C in which the substituents R ¹ to R ⁶ are all hydrogen atoms. , X / Y ≧ 7.4, and found that the coloring liquid satisfying the above-mentioned problem solves the above-mentioned problems, and completed the present invention.

More specifically, it is specific to compound A, which is a main colorant, by containing at least one compound selected from the group consisting of specific compound B and compound C having an anthraquinone skeleton in the molecule. It was possible to suppress crystal growth and contribute to the storage stability of the coloring liquid. By achieving this performance, it is possible to effectively prevent head filters, nozzle clogging, and the like when the coloring liquid is used as ink for an inkjet printer, which has a good effect on ink ejection stability.

In order to obtain a printed matter having high color development and saturation, it is preferable to use compound A alone, but from the viewpoint of the above-mentioned ejection stability, it is necessary to add compound B and / or compound C, and the compound It has been found that it is necessary to blend compound B and / or compound C in a specific ratio in order not to reduce the color development and saturation of the printed matter obtained from the coloring liquid using A. As a result, it was possible to obtain a printed material having good ejection stability and high color development and saturation.

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

1)
The water-insoluble colorant contains at least a water-insoluble colorant.
(A) Compound A, in which any one of the substituents ^R1 to R6 in the following formula ( ¹ ) is a cyano group and the other five are hydrogen atoms.
(B) Compound B in which at least ^two of the substituents ^R1 to R6 in the following formula (1) are cyano groups and all the substituents other than the cyano group are hydrogen atoms, in the following formula (1). The total mass X of the above (a) and the total mass Y of the above (b) include at least one compound selected from the group consisting of the compound C in which the substituents R ¹ to R ⁶ are all hydrogen atoms. , X / Y ≧ 7.4, a coloring liquid.

2)
The coloring liquid according to 1), wherein the compound A is a substituent R1 in the above formula ( ¹ ) being a cyano group.
3)
The coloring liquid according to 1) or 2), wherein the compound B is a substituent ^R1 and ^R2 in the above formula (1), respectively, as a cyano group.
4)
The coloring liquid according to any one of 1) to 3), which further contains a dispersant.
5)
The dispersant comprises a styrene- (meth) acrylic copolymer, a formarin condensate of aromatic sulfonic acid or a salt thereof, polyoxyethylene arylphenyl ether, polyoxyethylene arylphenyl ether sulfate, and polyoxyethylene naphthyl ether. The coloring solution according to 4), which comprises at least one selected from the group.
6)
The coloring solution according to 5), wherein the formalin condensate of aromatic sulfonic acid or a salt thereof contains a formalin condensate of creosote oil sulfonic acid or a salt thereof.
7)
5. The polyoxyethylene arylphenyl ether is described in 5) or 6), wherein the polyoxyethylene arylphenyl ether is a polyoxyethylene styrylphenyl ether and / or the polyoxyethylene arylphenyl ether sulfate is a polyoxyethylene styrylphenyl ether sulfate. Coloring liquid.
8)
The coloring liquid according to any one of 1) to 7), further containing a phytosterol compound.
9)
A coloring liquid set containing the coloring liquid according to any one of 1) to 8) and another coloring liquid.
10)
A recorded material obtained by using the coloring liquid according to any one of 1) to 8) or the coloring liquid set according to 9) with respect to the recording medium.
11)
The recording material according to 10), wherein the recording medium is a hydrophobic fiber.
12)
A printing step of adhering a droplet of the coloring liquid according to any one of 1) to 8) or a droplet of the coloring liquid set according to 9) to an intermediate recording medium to obtain a recorded image, and the intermediate recording medium. Of the hydrophobic fiber, comprising a transfer step of transferring the recorded image to the hydrophobic fiber by contacting the hydrophobic fiber with the adhering surface of the droplet of the coloring liquid or the coloring liquid set in the above and heat-treating. Printing method.

According to the present invention, it is possible to obtain a coloring liquid having high color development and saturation and excellent ejection stability.

Hereinafter, the present invention will be described in detail. In the present specification, "parts" and "%" are both based on mass, including examples and the like, unless otherwise specified. Further, "CI" is an abbreviation for a color index.

The colorant of the present invention contains at least a water-insoluble colorant, and the water-insoluble colorant is a water-insoluble colorant.
(A) Compound A in which any one of the substituents ^R1 to R6 in the above formula ( ¹ ) is a cyano group and the other five are hydrogen atoms.
(B) Compound B in which at least ^two of the substituents ^R1 to R6 in the above formula (1) are cyano groups and all the substituents other than the cyano group are hydrogen atoms, in the above formula (1). The total mass X of the above (a) and the total mass Y of the above (b) include at least one compound selected from the group consisting of the compound C in which the substituents R ¹ to R ⁶ are all hydrogen atoms. , X / Y ≧ 7.4, which is a coloring liquid.

[Compound A]
The compound A is not particularly limited as long as any one of the substituents ^R1 to R6 in the above formula ( ¹ ) is a cyano group and the other five are hydrogen atoms, and the above formula (1). It is preferable that R ¹ in the above is a cyano group. Compound A includes C.I. I. Disperse blue 359 is preferred. Compound A may be used alone or in combination of two or more.

[Compound B]
The compound B is not particularly limited as long as it is a compound in which at least ^two of the substituents ^R1 to R6 in the above formula (1) are cyano groups and all the substituents other than the cyano group are hydrogen atoms. Instead, it is preferable that R ¹ and R ² in the above formula (1) are cyano groups. Compound B may be used alone or in combination of two or more.

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

The compound represented by the above formula (1) is, for example, the above C.I. I. It can be obtained as a commercially available dye such as Disperse Blue 359. The compound B can be obtained by referring to, for example, Japanese Patent Publication No. 5-065358. The compound C can be obtained by referring to, for example, the non-patent document Zhurnal Organicheskoi Khimii Volume18 Issue7 Pages1539-49.

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

The coloring liquid may further contain a dispersant.

Examples of the dispersant include styrene- (meth) acrylic copolymer, formalin condensate of aromatic sulfonic acid or a salt thereof, polyoxyethylene arylphenyl ether, polyoxyethylene phenyl ether sulfate, polyoxyethylene naphthyl ether and the like. Can be used. The styrene- (meth) acrylic copolymer is a copolymer of a styrene-based monomer and a (meth) acrylic-based monomer. In addition, in this specification, "(meth) acrylic" means "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, and (α-methyl) styrene-methacrylic acid copolymer. Polymers, (α-methyl) styrene-methacrylic acid-acrylic acid ester copolymers, (α-methyl) styrene- (anhydrous) maleic acid copolymers, acrylic acid esters- (anhydrous) maleic acid copolymers, ( α-Methyl) styrene-acrylic acid ester- (anhydrous) maleic acid copolymer, acrylic acid ester-allylsulfonic acid ester copolymer, acrylic acid ester-styrenesulfonic acid copolymer, (α-methyl) styrene-methacryl Examples thereof include sulfonic acid copolymers, polyester-acrylic acid copolymers, polyester-acrylic acid-acrylic acid ester copolymers, polyester-methacrylic acid copolymers, polyester-methacrylic acid-acrylic acid ester copolymers; and the like. .. Among these, the compound containing an aromatic hydrocarbon group is preferably styrene. In addition, (α-methyl) styrene is used in the present specification as a meaning including α-methylstyrene and styrene. In the coloring liquid (dye dispersion liquid), the dispersant is a styrene- (meth) acrylic copolymer, a formarin condensate of aromatic sulfonic acid or a salt thereof, polyoxyethylene aryl phenyl ether, polyoxyethylene phenyl ether. Those containing at least one dispersant selected from the group consisting of sulfate and polyoxyethylene naphthyl ether are preferable. The content of the dispersant in the coloring liquid (dye dispersion liquid) is usually 1 to 36%, preferably 1 to 30%, more preferably 1 to 20%, still more preferably 1 to 15%.

Specific examples of the above-mentioned dispersant include Joncryl ^RTM 52J, 57J, 60J, 63J, 70J, JDX-6180, HPD-196, HPD96J, PDX-6137A, 6610, JDX-6500, JDX-6339, PDX-6102B, PDX. 6124, 67, 678, 680, 682, 683, 690 (manufactured by BASF) and the like can be mentioned, but the present invention is not limited thereto. In the present specification, the superscript RTM means 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 (styrene- (meth) acrylic copolymer, etc.) is measured by a GPC (gel permission chromatograph) method. The acid value of the styrene- (meth) acrylic copolymer used as the dispersant is preferably 50 to 250 mgKOH / g, more preferably 100 to 250 mgKOH / g, and particularly preferably 150 to 250 mgKOH / g. preferable. If the acid value becomes too small, the solubility of the dispersant (resin) in water deteriorates, and especially when the colorant is a dispersible dye, the dispersion stabilizing power tends to be inferior, and if the acid value becomes too large, it is aqueous. It has a strong affinity with the medium and tends to cause bleeding in the image after printing, which is not preferable. The acid value of the dispersant (resin) represents the number of mg of KOH required to neutralize 1 g of the dispersant (resin), and is measured according to JIS-K3054. Further, the glass transition temperature of the styrene- (meth) acrylic copolymer used as the dispersant is preferably 45 ° C to 135 ° C, more preferably 55 ° C to 120 ° C, and particularly preferably 60 to 110 ° C.

Specific examples of the styrene- (meth) acrylic copolymer which is a preferable dispersant in the above coloring liquid include Joncryl 67 (weight average molecular weight = 12,500, acid value = 213 mgKOH / g), 678 (weight average molecular weight =). 8,500, acid value = 215 mgKOH / g), 682 (weight average molecular weight = 1,700, acid value = 230 mgKOH / g), 683 (weight average molecular weight = 4,900, acid value = 215 mgKOH / g), 690 ( Weight average molecular weight = 16,500, acid value = 240 mgKOH / g) and the like, and Joncryl 678 is more preferable.

Dispersion of the colorant can be performed by, for example, the following method. A dispersant (styrene- (meth) acrylic copolymer, etc.) is added to a water-soluble organic solvent, the temperature is raised to 90-120 ° C. to prepare a dispersant solution, and an alkaline compound and water are added thereto. It is added to lower the temperature to obtain an emulsified (emulsion or microemulsion) liquid, and the prepared emulsion liquid and a colorant are mixed and dispersed.

The formalin condensate of the aromatic sulfonic acid or a salt thereof is an anionic surfactant obtained by the condensation reaction of the aromatic sulfonic acid and formalin. Examples of the "salt" include salts such as sodium salt, potassium salt and lithium salt. The formalin condensate of aromatic sulfonic acid or a salt thereof is referred to as a formalin condensate of aromatic sulfonic acid or a salt thereof or a mixture thereof (hereinafter, unless otherwise specified, "formalin condensate of sulfonic acid". , "The salt, or a mixture thereof" is also included) and the like are preferable. For example, cleosort oil sulfonic acid, cresol sulfonic acid, phenol sulfonic acid, β-naphthalen sulfonic acid, β-naphthol sulfonic acid, β-naphthalen sulfonic acid and β-naphthol sulfonic acid, benzene sulfonic acid, cresol sulfonic acid, 2- Examples thereof include formarin condensates such as naphthol-6-sulfonic acid, lignin sulfonic acid and methylnaphthalene sulfonic acid. Among these, each formarin condensate of cleosort oil sulfonic acid, β-naphthalene sulfonic acid, lignin sulfonic acid, and methylnaphthalene sulfonic acid is preferable. These are available as commercial products with various trade names. As an example, Demor N is used as a formalin condensate of β-naphthalene sulfonic acid, Demor C is used as a formalin condensate of creosote oil sulfonic acid; and Demor SN-B is used as a formalin condensate of special aromatic sulfonic acid. Kao Co., Ltd.); etc. Examples of the formalin condensate of creosote oil sulfonic acid include Laberin W series, and examples of the formalin condensate of methylnaphthalene sulfonic acid include Laberin AN series (both manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Among these, Demor N, Laberin AN series, and Laberin W series are preferable, Demor N and Laberin W are more preferable, and Labelin W is further preferable. Examples of the lignin sulfonic acid include Vanillex N, Vanillex RN, Vanillex G, Pearllex DP (all manufactured by Nippon Paper Industries, Ltd.) and the like. Among these, Vanillex RN, Vanillex N, and Vanillex G are preferable.

Examples of the polyoxyethylene arylphenyl ether include styrylphenol compounds such as polyoxyethylene styrylphenyl ether, polyoxyethylene distyrylphenyl ether, polyoxyethylene tristylylphenyl ether, and polyoxyethylene tetrastyrylphenyl ether; polyoxy. Benzylphenol compounds such as ethylenebenzylphenyl ether, polyoxyethylenedibenzylphenyl ether, polyoxyethylene tribenzylphenyl ether; cumylphenol compounds such as polyoxyethylene cumylphenyl ether; polyoxyethylene naphthylphenyl ether, polyoxyethylene Examples thereof include biphenyl ether and polyoxyethylene phenoxyphenyl ether. The number of repetitions of the polyoxyethylene group in the polyoxyethylene arylphenyl ether is preferably 1 to 30, more preferably 15 to 30. When the number of repetitions is 1 or more, the compatibility with an aqueous solvent or the like tends to be excellent. Further, when the number of repetitions is 30 or less, the viscosity tends not to be too high. Among the polyoxyethylene arylphenyl ethers, polyoxyethylene styrylphenyl ether is preferable. Commercially available products of polyoxyethylene styrylphenyl ether include, for example, Pionin D-6112, Pionin D-6115, Pionin D-6120, Pionin D-6131, Pionin D-6512, Takesurf D-6413, DTD-51, Pionin D. -6112, Pionin D-6320 (above, manufactured by Takemoto Oil & Fat Co., Ltd.); TS-1500, TS-2000, TS-2600, SM-174N (above, manufactured by Toho Chemical Industry Co., Ltd.); Emargen A-60, Emargen A- 90, Emalgen A-500 (all manufactured by Kao Corporation); and the like.

Examples of the polyoxyethylene aryl phenyl ether sulfate include the above-mentioned polyoxyethylene styryl phenyl ether sulfate and the like. Among the above-mentioned polyoxyethylene arylphenyl ether sulfates, polyoxyethylene styrylphenyl ether sulfate is preferable. Examples of commercially available products of polyoxyethylene styrylphenyl ether sulfate include SM-57, SM-210 (all manufactured by Toho Chemical Industry Co., Ltd.) and the like.

Examples of the commercially available polyoxyethylene naphthyl ether include Neugen EN series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and Pionin D-7240 (manufactured by Takemoto Oil & Fats Co., Ltd.).

It is one of the preferable forms that the polyoxyethylene arylphenyl ether is polyoxyethylene styrylphenyl ether and / or the polyoxyethylene arylphenyl ether sulfate is polyoxyethylene styrylphenyl ether sulfate. be.

The coloring liquid may further contain a conventionally known nonionic dispersant in addition to the dispersant. Examples of the nonionic dispersant include alkylene oxide adducts of cholestanols, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene. Examples thereof include alkylamines, glycerin fatty acid esters, oxyethylene oxypropylene block polymers, and substituted derivatives thereof. As the alkylene oxide adduct of cholestanols, the C2-C4 alkylene oxide adduct of cholestanols is preferable, and the ethylene oxide adduct is more preferable. In the present specification, "cholestanols" is used as a meaning including both "cholestanol" and "hydrogenated cholestanol". For example, examples of ethylene oxide adducts of cholestanols include ethylene oxide adducts of cholestanol and ethylene oxide adducts of hydrogenated cholestanol. The amount of alkylene oxide (preferably C2-C4 alkylene oxide, more preferably ethylene oxide) added per mol of cholestanols is preferably about 10 to 50 mol, and the HLB is preferably about 13 to 20 mol.

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

The coloring liquid may further contain water.

The above water is preferably water with few impurities such as ion-exchanged water and distilled water. Further, the colored liquid can be subjected to microfiltration using a membrane filter or the like. When the colorant is used for inkjet printing ink, it is preferable to perform microfiltration for the purpose of preventing nozzle clogging and the like. The pore size of the filter used for microfiltration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

The coloring liquid may further contain a phytosterol-based compound.
The phytosterol-based compound represents a compound having a phytosterol skeleton in the molecule, and examples thereof include alkylene oxide adducts of phytosterols. As the phytosterol alkylene oxide adduct, the C2-C4 alkylene oxide adduct of the phytosterols is preferable, and the ethylene oxide adduct is more preferable. In the present specification, "phytosterols" is used as a meaning including both "phytosterols" and "hydrogenated phytosterols". For example, examples of the ethylene oxide adducts of phytosterols include ethylene oxide adducts of phytosterols and ethylene oxide adducts of hydrogenated phytosterols. The amount of alkylene oxide (preferably C2-C4 alkylene oxide, more preferably ethylene oxide) added per mol of phytosterols is preferably about 10 to 50 mol, and the HLB is preferably about 13 to 20 mol. Commercially available products of phytosterol alkylene oxide adducts include, for example, NIKKOL BPS-20, NIKKOL BPS-30 (all manufactured by Nikko Chemicals Co., Ltd., phytosterol ethylene oxide adduct), and NIKKOL BPSH-25 (hydrogenated). Phytosterol ethylene oxide adduct) and the like. Examples of commercially available products of alkylene oxide adducts of cholestanols include NIKKOL DHC-30 (manufactured by Nikko Chemicals Co., Ltd., ethylene oxide adducts of cholestanol), and NIKKOL BPS-30 is preferable.

The coloring liquid can further contain additives.

Examples of the additive include a surfactant, a water-soluble organic solvent, a preservative, a pH adjuster, a chelating reagent, a rust preventive, a water-soluble ultraviolet absorber, a water-soluble polymer compound, a viscosity regulator, and a dye-dissolving agent. , Anti-fading agents, antioxidants and the like.

Examples of the above-mentioned surfactant include known surfactants such as anionic type, cationic type, amphoteric type, nonionic type, silicone type and fluorine type. Examples of the anionic surfactant include alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acylamino acids and salts thereof, N-acylmethyl taurine salts, and alkyl sulfates. Polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, loginate soap, castor oil sulfate ester salt, lauryl alcohol sulfate ester salt, alkylphenol type phosphoric acid ester, alkyl type phosphoric acid ester, alkylaryl sulfonate, Examples thereof include diethyl sulfo sulphate, diethyl hexyl sulfo sulphate, and dioctyl sulphonic sulphate. Specific examples of the commercially available products include, for example, High Tenor LA-10, LA-12, LA-16, Neo High Tenor ECL-30S, and ECL-45 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. Examples of the cationic surfactant include a 2-vinylpyridine derivative and a poly4-vinylpyridine derivative. Examples of the amphoteric tenside include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amide propyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and imidazoline derivatives. Can be mentioned. Examples of the nonionic surfactant include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether; Esters such as polyoxyethylene oleic acid ester, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-Tetramethyl-5-decine-4,7-diol, 3,6-dimethyl-4-octin-3,6-diol, 3,5-dimethyl-1-hexin-3-ol Etc. acetylene glycol (alcohol) -based; Nisshin Chemical Co., Ltd., trade names Surfinol 104, 105, 82, 465, Orphine STG, etc .; Polyglycol ether-based (for example, Tergitol 15-S-7 manufactured by SIGMA-ALDRICH), etc. ); And so on.

Examples of the silicone-based surfactant include polyether-modified siloxane, polyether-modified polydimethylsiloxane, and the like. Specific examples of commercially available products include BYK-347 (polyether-modified siloxane); BYK-345, BYK-348 (polyether-modified polydimethylsiloxane), all of which are manufactured by Big Chemie. Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group. Examples thereof include a polyoxyalkylene ether polymer compound contained in. Specific examples of commercially available products include, for example, Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30, FS-31 (manufactured by DuPont); PF-151N. , PF-154N (manufactured by Omniova) and the like.

The water-soluble organic solvent is not particularly limited, and examples thereof include glycol-based solvents, polyhydric alcohols, and pyrrolidones. Glycer-based solvents include glycerin, polyglycerin (# 310, # 750, # 800,), diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, and un. Examples thereof include compounds such as decaglycerin, dodecaglycerin, tridecaglycerin, tetradecaglycerin, and mixtures thereof. Examples of polyhydric alcohols include C2-C6 polyhydric alcohols having 2 to 3 alcoholic hydroxyl groups, di or tri-C2-C3 alkylene glycols, or poly-C2 having 4 or more repeating units and a molecular weight of about 20,000 or less. ~ C3 alkylene glycol, preferably liquid polyalkylene glycol and the like can be mentioned. Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, thiodiglycol, and 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 Examples thereof include -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, 1- (2-hydroxyethyl) -2-pyrrolidone and the like. The water-soluble organic solvent preferably contains at least either glycerin or diglycerin. In addition, compounds that dissolve in water and serve as a wetting agent are also included in the water-soluble organic solvent in the present invention for convenience, and examples thereof include urea, ethylene urea, and saccharides. Considering storage stability, when the water-insoluble colorant is a disperse dye or an oil-soluble dye, a solvent having a low solubility thereof is preferable, and among these, a solvent other than glycerin and a solvent other than glycerin (preferably a polyhydric substance other than glycerin) is preferable. It is preferable to use it in combination with alcohol). The total content of the water-soluble organic solvent in the total mass of the coloring liquid is usually 5 to 50%, and it is preferable to add 10 to 40%.

Examples of the preservative include organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, haloallyl sulfone-based, iodopropagil-based, N-haloalkylthio-based, nitrile-based, pyridine-based, 8-oxyquinolin-based, and benzo. Thiazole-based, isothiazolin-based, dithiol-based, pyridineoxide-based, nitropropane-based, organic tin-based, phenol-based, tetraammonium salt-based, triazine-based, thiazine-based, anilide-based, adamantan-based, dithiocarbamate-based, brominated indanone-based. , Benzyl bromacetate-based, inorganic salt-based compounds and the like. Specific examples of the organic halogen-based compound include pentachlorophenol sodium, and specific examples of the pyridine oxide-based compound include, for example, 2-pyridinethiol-1-oxide sodium, and specific examples of the isothiazolinone-based compound. Examples 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-onemagnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-onecalcium chloride, 2-methyl-4-isothiazolin-3-onecalcium chloride and the like can be mentioned. .. Specific examples of other preservatives (preservatives and fungicides) include acetic anhydride, sodium sorbate or sodium benzoate, manufactured by Ronza, trade names Proxel ^RTM GXL (S) and Proxel ^RTM XL-2 (S). Can be mentioned.

As the pH adjuster, any substance can be used as long as the pH of the solution can be controlled in the range of approximately 5 to 11 without adversely affecting the adjusted coloring liquid. Specific examples thereof include alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water). Alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate; alkali metal salts of organic acids such as potassium acetate; inorganic bases such as sodium silicate and disodium phosphate, etc. Ethanolamine is preferred.

Specific examples of the chelating reagent include sodium ethylenediamine tetraacetate, sodium nitrilo triacetate, sodium hydroxyethylethylenediamine triacetate, sodium diethylenetriamine pentaacetate, sodium uracil diacetate and the like.

Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglucolate, diisopropylammonium nitrate, pentaerythritol tetranitrate, dicyclohexylammonium nitrate and the like.

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

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

Examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, and examples thereof include polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

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

The above anti-fading agent is used for the purpose of improving the storage stability of the image. As the anti-fading agent, various organic and metal complex-based anti-fading agents can be used. Examples of the organic system include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromanes, alkoxyanilines, heterocyclics and the like. Examples of the metal complex system include nickel complexes and zinc complexes.

As the above-mentioned antioxidant, for example, various organic and metal complex-based antioxidants can be used. Examples of the organic antioxidants include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles and the like. ..

The coloring liquid preferably contains at least one selected from the group consisting of a water-soluble organic solvent, a preservative, and a pH adjuster as the additive.

The coloring liquid may further contain a resin emulsion.

Examples of the resin emulsion include acrylic resin, epoxy resin, urethane resin, polyether resin, polyamide resin, unsaturated polyester resin, phenol resin, silicone resin, fluororesin, and polyvinyl resin (eg, polyvinyl chloride and polyvinyl acetate). , Polyvinyl alcohol, etc.), alkyd resin, polyester resin, or amino material (melanin resin, urea resin, urea resin, melanin formaldehyde resin, etc.). Moreover, those emulsions may be composed of two or more kinds of resins. Further, a composite resin in which two or more kinds of resins form a core / shell structure may be used. Among these resin emulsions, urethane resin is preferable for use in the above-mentioned coloring liquid.

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

The urethane resin emulsion preferably has an SP value (solubility parameter) of 8 to 24, more preferably 8 to 17, and particularly preferably 8 to 11. When the resin in the urethane resin emulsion has an acidic group, the SP value of the resin before neutralization is used when the emulsion is produced by neutralizing the acidic group.

When the urethane resin emulsion has acidic groups such as carboxylic acid, sulfonic acid, and hydroxyl group, those acidic groups may be alkaline chloride. Alkaline chloride can be carried out by, for example, the following method. Examples thereof include a method in which a urethane resin emulsion having an acidic group is added to water and stirred to prepare an aqueous solution, and an alkaline compound is added to the aqueous solution to prepare a solution having a pH adjusted to 6.0-12.0.

Examples of the alkaline compound include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and alkaline earth metals such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide and strontium hydroxide. Hydroxides, triethylamine and the like can be mentioned. Only one kind of these alkaline compounds may be used, or two or more kinds thereof may be used in combination.

Examples of the method for preparing the coloring liquid include a method of mixing the above-mentioned components. The order in which the components are mixed is not particularly limited.

The coloring liquid may be used as it is as an ink, or water, a dispersant, a surfactant, a pH adjusting agent, an additive, etc. may be added to the coloring liquid as it is, or an amount may be added to make an ink. You can also do it.

As a method for dispersing the coloring liquid, for example, a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a high-pressure emulsifier, or the like is used to stir and mix each component constituting the coloring liquid. Method can be mentioned. As an example, when a sand mill is used, first, each component and beads as a dispersion medium are charged into the sand mill. As the beads, glass beads having a particle diameter of 0.01 to 1 mm, zirconia beads and the like can be used. The amount of beads used is preferably 2 to 6 parts by mass with respect to 1 part by mass of the dispersion target. Next, the sand mill is operated to perform the distributed processing. The dispersion treatment conditions are preferably about 1000 to 2000 rpm for 1 to 20 hours. Then, by removing the beads by filtration or the like after the dispersion treatment, a dispersed coloring liquid can be obtained.

The colorant may be mixed and dispersed at the time of dispersion to obtain a coloring liquid, or a liquid in which water-insoluble colorants are dispersed may be mixed.

The dyeing bath for dyeing containing the above coloring liquid is also included in the present invention.

The prepared coloring liquid may be microfiltered using a membrane filter or the like. In particular, when the coloring liquid is used as an ink for inkjet printing, it is preferable to perform microfiltration for the purpose of preventing nozzle clogging and the like. The pore size of the filter used for microfiltration is usually 0.1 to 1 μm, preferably 0.1 to 0.8 μm.

The above-mentioned inkjet printing ink (hereinafter, may be abbreviated as ink) has a viscosity at 25 ° C., which is usually 3 to 3 when measured with an E-type viscometer, from the viewpoint of high-speed ejection response. It is preferably about 20 mPa · s. The surface tension is preferably in the range of 20 to 45 mN / m when measured by the plate method. It is preferable to adjust each of these values so as to be an appropriate value in consideration of the ejection amount of the printer to be used, the response speed, the ink droplet flight characteristics, and the like.

A coloring liquid set containing the coloring liquid and another coloring liquid, and an ink when the coloring liquid is used as an ink for inkjet printing and another ink when the other coloring liquid is used as an ink for inkjet printing. The including ink set is also included in the present invention.
The above-mentioned other inks represent inks having a composition and hue different from those of the above-mentioned inks, and are, for example, yellow ink, magenta ink, black ink, orange ink, violet ink, turquoise ink, blue ink, fluorescent pink ink, and fluorescent yellow ink. Etc., but not as shown here. Further, a low-concentration ink or a high-concentration ink in which the total concentration of the colorant in the ink is changed may be used with respect to the above-mentioned ink or the above-mentioned other ink, and examples of the low-concentration ink include light yellow ink and light. Examples thereof include magenta ink, light cyan ink, and light black ink. When constituting the above ink set, for example, one kind of colorant may be contained in the ink of each color, or two or more kinds may be used in combination. The colorant contained in each ink constituting the ink set may be known and is not particularly limited.

Examples of the colorant that may be contained in the above-mentioned other inks include disperse dyes and oil-soluble dyes, and specific examples of the disperse dyes include C.I. 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, 122, 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. 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 threads 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, 127,128,131,132,134,135,137,143,145,146,151,152,153,154,157,159,164,167,169,177,179,181,183,184,185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 289, 298, 302, 303, 310, 311, 312, 320, 324, 328, 343, 362, 364, etc .; 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. I. Disperse Green 6: 1, 9 etc .; C.I. I. Disperse brown 1, 2, 4, 9, 13, 19, 26, 27, etc .; C.I. 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, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211. , 214, 224, 225, 257, 259, 267, 268, 270, 284, 285, 287, 288, 291, 293, 295, 297, 301, 315, 330, 332, 333, 334, 343, 359, 360. Etc.; C.I. I. Disperse black 1, 3, 10, 24, etc.; etc.

Specific examples of the oil-soluble dye include C.I. 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. I. Solvent orange 1, 2, 14, 45, 60, etc .: C.I. 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. I. Solvent green 3rd grade: C.I. I. Solvent Braun 3, 5 etc .: C.I. 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. 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 described above may be used alone or in combination of two or more.

The present invention also includes a recorded material obtained by using (for example, attaching) the coloring liquid or the coloring liquid set to a recording medium.

The recording medium is not particularly limited as long as it can be recorded using the coloring liquid or an ink containing the coloring liquid, and examples thereof include paper, cloth, and the like, and the cloth, particularly hydrophobic fiber. Is preferable.

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. Further, a blended fiber of these and a regenerated fiber such as rayon or a natural fiber such as cotton, silk and wool is also included in the hydrophobic fiber in the present specification. As these hydrophobic fibers, those having an ink receiving layer (bleeding prevention layer) are also known, and such hydrophobic fibers are also included. The method for forming the ink receiving layer is a known technique, and fibers having an ink receiving layer are also available as commercial products. The material and structure of the ink receiving layer are not particularly limited, and can be appropriately used depending on the purpose and the like.

Although the coloring liquid can be used in various fields, it is suitable for water-based writing inks, water-based printing inks, information recording inks, printing, etc., and is particularly preferably used as inkjet printing inks.

A printing step of adhering a droplet of the coloring liquid or the coloring liquid set to an intermediate recording medium to obtain a recorded image, and adhesion of the coloring liquid or the droplet of the coloring liquid set on the intermediate recording medium. The present invention also includes a transfer step of transferring the recorded image to the hydrophobic fiber by bringing the hydrophobic fiber into contact with the surface and heat-treating the surface, and a method for printing the hydrophobic fiber including the transfer step. Further, the present invention also includes an intermediate recording medium to which the coloring liquid or the droplets of the coloring liquid set are attached.

The above-mentioned method for printing hydrophobic fibers is roughly classified into two types. The first method is a method called direct printing or direct printing, in which the coloring liquid or the droplets of the coloring liquid set are attached to the hydrophobic fibers by an inkjet printer. Step A for forming image information such as characters and patterns on hydrophobic fibers, and the coloring liquid attached by the step A, or the sublimating dye (water-insoluble coloring agent) in the droplets of the coloring liquid set. It is a method for printing a hydrophobic fiber, which comprises at least three steps of a step B of fixing to the fiber by heat and a step C of cleaning the unfixed sublimation dye remaining in the fiber. Step B is generally performed by known steaming or baking. The steaming includes, for example, a high temperature steamer usually at 170 to 180 ° C. for about 10 minutes; and a high pressure steamer usually at 120 to 130 ° C. for about 20 minutes; a sublimation dye by a method for treating hydrophobic fibers. Is dyed on the fiber (also called moist heat fixation). As baking (thermosol), a sublimation dye is dyed on the fiber by a method of treating the hydrophobic fiber, for example, usually at 190 ° C to 210 ° C, usually about 60 to 120 seconds (also called dry heat fixation). The method can be mentioned. Step C is a step of washing the obtained fibers with warm water and, if necessary, water. The warm water or water used for washing may contain a surfactant. It is also preferable to dry the washed fibers at 50 to 120 ° C. for 5 to 30 minutes. The second method is a method called sublimation transfer printing, sublimation transfer printing, etc., in which the coloring liquid or droplets of the coloring liquid set are adhered to an intermediate recording medium by an inkjet printer. After obtaining a recorded image such as characters and patterns, the hydrophobic fiber is brought into contact with the adhesion surface of the coloring liquid or the droplet of the coloring liquid set in the intermediate recording medium and heat-treated to be intermediate. This is a method for printing hydrophobic fibers, in which recorded images such as characters and patterns recorded on a recording medium are transferred to hydrophobic fibers. As the intermediate recording medium, the coloring liquid adhering to the intermediate recording medium or the sublimation dye (water-insoluble colorant) in the coloring liquid set does not aggregate on the surface of the intermediate recording medium, and the image is recorded on hydrophobic fibers. Those that do not interfere with the sublimation of the dye during transfer are preferred. An example of such an intermediate recording medium is a paper having a dye dispersion receiving layer formed on the surface of inorganic fine particles such as silica, and a special paper for inkjet can be used. Examples of the heat treatment for transferring the recorded image from the intermediate recording medium to the hydrophobic fiber include a dry heat treatment at about 190 to 200 ° C.

As the dyeing method by the above dyeing, the hydrophobic fiber is immersed in the coloring liquid of the present invention and dyed under pressure at preferably 105 ° C. or higher, more preferably 110 to 140 ° C., preferably 30 minutes to 1 hour. can. Particularly preferably, it can be stained at 120 to 130 ° C. for 30 to 45 minutes. It can also be dyed in the presence of carriers such as o-phenylphenol and trichlorobenzene, for example, in the boiling state of water. Alternatively, dyeing by a so-called thermosol method, in which the coloring liquid of the present invention is padded on hydrophobic fibers and subjected to a dry heat treatment at 150 to 230 ° C., is also possible.

The above printing method may further include a fiber pretreatment step for the purpose of preventing bleeding and the like. As this pretreatment step, an aqueous solution containing at least one kind of paste, an alkaline substance, an antioxidant and a hydrotropy agent is applied to the coloring liquid or the fiber before attaching the ink containing the coloring liquid. Can be mentioned. As a step of applying the pretreatment, it is preferable to use an aqueous solution of the pretreatment agent containing a glue, an alkaline substance, an antioxidant and a hydrotropy agent as the pretreatment liquid, and impregnate the pretreatment liquid with fibers. Examples of the adhesive include natural gums such as guar and locust beans, starches, sodium alginate, seaweeds such as furinate, plant skins such as pectic acid, methyl fiber, ethyl fiber, hydroxyethyl cellulose, carboxymethyl cellulose and the like. Examples thereof include fiber element derivatives of the above, processed starches such as carboxymethyl starch, synthetic glues such as polyvinyl alcohol and polyacrylic acid esters, and the like. Preferred is sodium alginate.

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, and include inorganic or organic alkali metal hydroxides and alkalis. Metal salts are preferable, and examples thereof include sodium compounds and potassium compounds. Specific examples include alkali metal hydroxides such as sodium hydroxide and calcium hydroxide, and inorganic compounds such as sodium carbonate, sodium hydrogencarbonate, potassium carbonate, sodium dihydrogen phosphate, disodium hydrogenphosphate, and sodium phosphate. Alkali metal salts, alkali metal salts of organic compounds such as sodium formate, sodium trichloracetate; and the like. Preferred is sodium hydrogen carbonate. As the reduction inhibitor, sodium metanitrobenzenesulfonate is preferable. Examples of the hydrotropy agent include ureas such as urea and dimethylurea, and urea is preferable. As the above-mentioned adhesive, alkaline substance, antioxidant, and hydrotropy agent, a single compound may be used, or a plurality of compounds may be used in combination. The mixing ratio of each pretreatment agent in the total mass of the pretreatment liquid is, for example, 0.5 to 5% for the sizing agent and 0.5 to 5% for the alkaline substance (sodium hydrogen carbonate, etc.) based on the mass. , Anti-reduction agent (sodium metanitrobenzene sulfonate, etc.) is 0 to 5%, hydrotropy agent (urea, etc.) is 1 to 20%, and the balance is water. The application of the pretreatment agent to the cellulosic fiber may be, for example, a padding method. The squeezing ratio of the padding is preferably about 40 to 90%, more preferably about 60 to 80%.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to Examples. Unless otherwise specified in the examples, "parts" means parts by mass and "%" means parts by mass. The inks in each embodiment are included in the coloring liquid.

The compounds represented by the following formula (B-1) and the following formula (C-1) are prepared with reference to the methods described in JP-A-5-06558, non-patent document Zhurnal Organicheskoi Khimii Volume18 Issue7 Pages1539-49, respectively. Was done.

[Preparation Example 1: Preparation of Emulsion Solution of Joncryl 678]
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 temperature was raised to 90 to 120 ° C. Then, the mixture was stirred for 5 hours to obtain an emulsion solution of Joncryl 678.

[Preparation Example 2: Preparation of Aqueous Dispersion Solution 1]
As a colorant, commercially available C.I. I. Disperse Blue 359 (10 parts), Laberin W-40 (Aqueous solution of sodium sulfonic acid sulfonic acid polycondensate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (15 parts), NIKKOL BPS-30 (ethylene oxide adduct of phytosterol) , Nikko Chemicals Co., Ltd. (0.8 parts), Surfinol 104PG50 (Surfinol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted with propylene glycol to a concentration of 50%) (0. Add 0.2 mm diameter glass beads to a mixture consisting of 2 parts), Proxel GXL (S) (manufactured by Ronza) (0.1 parts), and ion-exchanged water (73.9 parts), and cool with a sand mill. The dispersion treatment was carried out for about 15 hours. The obtained liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size: 0.5 μm) to obtain an aqueous dispersion liquid 1.

[Preparation Example 3: Preparation of Aqueous Dispersion Liquid 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 (10 parts) represented by the formula (B-1).

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

[Preparation Example 5: Preparation of Aqueous Dispersion Liquid 4]
C. as a colorant. I. Disperse Blue 359 (10 parts), Joncryl 678 emulsion (30 parts), Surfinol 104PG50 (Surfinol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted to 50% concentration with propylene glycol). 0.2 mm diameter glass beads were added to the mixture consisting of (0.2 parts), Propylene GXL (S) (manufactured by Ronza) (0.1 parts), and ion-exchanged water (59.7 parts). The dispersion treatment was carried out for about 15 hours under cooling with a sand mill. The obtained liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size: 0.5 μm) to obtain an aqueous dispersion liquid 4.

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

[Preparation Example 7: Preparation of Aqueous Dispersion Solution 6]
C. as a colorant. I. Disperse Blue 359 (10 parts), SM-57 (manufactured by Toho Chemical Industry Co., Ltd., polyoxyethylene styrylphenyl ether sulfate-based dispersant) (10 parts), Surfinol 104PG50 (Surfinol 104 (acetylene glycol surfactant,) Air Products Japan Co., Ltd.) diluted to 50% concentration with propylene glycol) (0.2 parts), Proxel GXL (S) (manufactured by Ronza Co., Ltd.) (0.1 parts), and ion-exchanged water (79. 0.2 mm diameter glass beads were added to the mixture consisting of 7 parts), and the mixture was subjected to dispersion treatment for about 15 hours under cooling with a sand mill. The obtained liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size: 0.5 μm) to obtain an aqueous dispersion liquid 6.

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

[Preparation Example 9: Preparation of Examples and Comparative Examples]
Using the aqueous dispersions 1 to 7 obtained above, mix with each component as shown in Table 1 below, stir for 30 minutes, and then glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore diameter: 0). Each ink of Examples 1 to 11 and Comparative Examples 1 and 2 was prepared by filtering with a diameter of .5 μm). In the table, the numerical value of each component indicates the number of copies added.

The abbreviations, etc. in Table 1 below indicate the following.
Proxel GXL: Lonza, Prokiquil GXL (S), Preservative Surfinol 465: Nissin Chemical Industry, nonionic surfactant TEA-80: 80% aqueous solution of triethanolamine X / Y: Above (a) Total mass X / total mass Y in (b) above, a value calculated by the relational expression

Using the ink prepared as described above, each of the following evaluation tests was performed. The evaluation results are shown in Table 1. "N / A" in Table 1 indicates that it is not applicable.

[Intermediate recording medium printed with ink and sublimation transfer printing using it]
Each of the prepared inks is filled in an inkjet printer (manufactured by EPSON Co., Ltd., trade name PX-504A), and using TRANSJET EcoII 8385 (95 g / m ² ) as an intermediate recording medium, from 0% to 100% Duty, 5 Intermediate recording media on which gradation images in% Duty increments were printed were obtained. After superimposing the colored liquid adhering surface of each of the obtained intermediate recording media and the polyester cloth (Teijin Tropical), a tabletop automatic flat press machine (manufactured by Asahi Textile Machinery Co., Ltd .: AF-65TEN) was used at 200 ° C. × 60. By heat-treating under the condition of seconds, dyed products dyed by the sublimation transfer dyeing method were obtained. The following evaluations were performed on each of the obtained dyed products.

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

[Evaluation of color development]
The dyed portion of 100% Duty of each of the obtained dyed products was color-measured using a spectrophotometer "Ci62 (manufactured by X-Rite)", and the concentration of each dyed product was measured. Color measurement was performed under the conditions of D65 light source, viewing angle 2 °, and status T. The reflectance R of each dyed product at 400 to 700 nm is measured, the K / S value is calculated by the Kubelka-Munk formula: K / S = (1-R) ² / 2R, and the K / S value at each wavelength is further calculated. The sigma K / S value, which is the total of the values, was calculated. The larger the sigma K / S value, the higher the color density and the higher the 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 and less than 210.
C: 190 or more and less than 200.
D: Less than 190.

[Evaluation of discharge stability]
Each ink was filled in the inkjet printer, and it was confirmed that there were no nozzles that were clogged and that recording could be performed from all the nozzles. The cartridge containing the ink was taken out and left in an environment of 60 ° C. for 14 days. These were refilled in an inkjet printer, cleaned twice and printed on 100 sheets, and a check pattern was printed. The number of white spots in the check pattern was counted. The larger the number of white spots, the worse the storage stability of the ink, and the worse the ejection stability during printing. Evaluation was made according to the following evaluation criteria.
[Evaluation criteria]
A: Less than two.
B: 2 or more and less than 4.
C: 4 or more, less than 6.
D: 6 or more.

As is clear from the evaluation results in Table 1, the prepared inks of Examples 1 to 12 have higher saturation, better ejection stability, and higher color development than the inks of Comparative Examples 1 to 4. ing.

The coloring liquid of the present invention can obtain a high-quality cyan to blue dyed product having high color development and saturation and good ejection stability, and is required as various printing inks, especially inkjet printing inks. It is extremely useful as a cyan ink for inkjet printing for sublimation transfer because it can maintain printability.

Claims (12)

1. The water-insoluble colorant contains at least a water-insoluble colorant.
   (A) Compound A, in which any one of the substituents ^R1 to R6 in the following formula ( ¹ ) is a cyano group and the other five are hydrogen atoms.
   (B) Compound B in which at least ^two of the substituents ^R1 to R6 in the following formula (1) are cyano groups and all the substituents other than the cyano group are hydrogen atoms, in the following formula (1). The total mass X of the above (a) and the total mass Y of the above (b) include at least one compound selected from the group consisting of the compound C in which the substituents R ¹ to R ⁶ are all hydrogen atoms. , X / Y ≧ 7.4, a coloring liquid.
   

   
2. The coloring liquid according to claim 1, wherein the compound A is a cyano group as the substituent ^R1 in the above formula (1).
3. The coloring liquid according to claim 1 or 2, wherein the compound B is a substituent R ¹ and R ² in the above formula (1), respectively.
4. The coloring liquid according to any one of claims 1 to 3, further comprising a dispersant.
5. The dispersant comprises a styrene- (meth) acrylic copolymer, a formarin condensate of aromatic sulfonic acid or a salt thereof, polyoxyethylene arylphenyl ether, polyoxyethylene arylphenyl ether sulfate, and polyoxyethylene naphthyl ether. The coloring solution according to claim 4, which comprises at least one selected from the group.
6. The coloring liquid according to claim 5, wherein the formalin condensate of the aromatic sulfonic acid or a salt thereof contains the formalin condensate of creosote oil sulfonic acid or a salt thereof.
7. The fifth or six claim, wherein the polyoxyethylene arylphenyl ether is a polyoxyethylene styrylphenyl ether and / or the polyoxyethylene arylphenyl ether sulfate is a polyoxyethylene styrylphenyl ether sulfate. Coloring liquid.
8. The coloring liquid according to any one of claims 1 to 7, further comprising a phytosterol-based compound.
9. A coloring liquid set containing the coloring liquid according to any one of claims 1 to 8 and another coloring liquid.
10. A recorded material obtained by using the coloring liquid according to any one of claims 1 to 8 or the coloring liquid set according to claim 9 for a recording medium.
11. The recorded material according to claim 10, wherein the recording medium is a hydrophobic fiber.
12. A printing step of adhering a droplet of the coloring liquid according to any one of claims 1 to 8 or the coloring liquid set according to claim 9 to an intermediate recording medium to obtain a recorded image, and the intermediate recording. Hydrophobic fibers comprising a transfer step of transferring the recorded image to the hydrophobic fibers by contacting the hydrophobic fibers with the adhering surface of the colored liquid or the droplet of the colored liquid set in the medium and heat-treating the colored liquid. Printing method.