JP7504698B2 - Coloring solution and textile printing method - Google Patents

Description

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

In recent years, a recording method for plateless printing using inkjet printing has been proposed, and inkjet printing is also used for printing on fibers, including cloth. Compared to conventional printing methods such as screen printing, inkjet printing has various advantages, such as no platemaking, resource saving, energy saving, and ease of high-resolution expression. Here, hydrophobic fiber fabrics such as polyester fibers are generally dyed with colorants that are insoluble in water. Therefore, as an aqueous ink for printing hydrophobic fibers using inkjet recording methods, it is generally necessary to use a dispersion ink in which a water-insoluble colorant is dispersed in water and which has good performance such as dispersion stability. Inkjet printing methods for hydrophobic fibers, such as polyester fibers, can be broadly divided into the following two methods. The direct printing method involves printing ink directly onto the fibers, then subjecting the dye in the ink to heat treatment such as high-temperature steaming to dye the fibers. The sublimation transfer method involves printing ink onto an intermediate recording medium (such as special transfer paper), then overlapping the ink-applied surface of the intermediate recording medium with hydrophobic fibers, and then using heat to transfer the dye from the intermediate recording medium to the fibers.

The inkjet inks used are mainly water-based inks, in which sublimation dyes selected from the water-insoluble disperse dye group and oil-soluble dye group are dispersed in water to form a dye dispersion liquid, which is stabilized as fine particles using a dispersant, and the ink is made by optimizing the physical properties (physical properties) such as particle size, viscosity, surface tension, and pH using a water-soluble organic solvent as a humectant (anti-drying agent), a surfactant as a surface tension adjuster, and other additives (pH adjusters, preservatives/anti-fungal agents, defoamers, etc.) (see Patent Document 1).

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 suitable for transfer to polyester by heat treatment. The processing steps are as follows:
(1) Printing step: applying dye ink to an intermediate recording medium by an inkjet printer;
(2) Transfer process: A process 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.

This method has attracted a lot of attention because it does not require water, making it easy to dye, and because of the recent interest in environmental issues related to wastewater. However, unlike conventional dyeing, it does not penetrate deep into the fabric, and dyes only the surface of the non-dyed object, which means that the dyeing concentration (color development) appears low. In particular, with black ink, various companies are working on improving color development. (See Patent Document 2) In addition, there is a demand for black ink that does not vary in black hue depending on the sublimation transfer conditions and has a uniform sublimation speed.

When using dyes with sublimation properties to produce black, multiple dyes are usually combined to produce black. This is because a single dye is often insufficient to produce a black hue and is often low in concentration, so a combination of multiple dyes allows for a good black hue to be produced. However, when dyeing fabric with a black ink that combines multiple dyes with sublimation properties, depending on the type of fabric, the black hue produced on the fabric may appear different when the fabric is irradiated with light from a light source with a different spectral distribution. For example, even if a good color can be produced under lighting with little long-wavelength light, such as fluorescent lighting, it may appear reddish under sunlight with a lot of long-wavelength light, or conversely, even if a good color can be produced under sunlight, it may appear bluish under fluorescent lighting. In this way, the characteristics that affect the appearance of the color of an object due to the lighting source are generally called "color rendering," and there has been a demand for a black ink that has little change in hue due to the influence of color rendering.

On the other hand, in the sublimation transfer printing method for hydrophobic fibers, sublimation transfer ink is applied (printed) to an intermediate recording medium (specialized transfer paper, etc.) by an inkjet printer, and the ink-applied (printed) surface of the intermediate recording medium is superimposed on the object to be dyed (polyester fiber, etc.), and the sublimation dye is transferred to the object to be dyed by a heat pressing method using a heat pressing roller or a heat press machine. In commercial printing, inkjet printing is becoming faster, and inkjet inks that can be designed to accommodate higher speeds are also required. In addition, as an intermediate recording medium for sublimation transfer ink, inkjet paper with an ink-receiving layer formed on the surface with inorganic fine particles such as silica and a relatively large basis weight so that a large amount of ink can be applied is generally mentioned, but in recent years, transfer paper with a smaller basis weight or transfer paper with a smaller ink-receiving layer has been used, and there is a strong demand for high transfer efficiency and high dyeing density with a small amount of ink. In addition, there is a demand for black ink that does not vary in black hue depending on the sublimation transfer conditions, has a uniform sublimation speed, and has little hue variation due to the influence of color rendering. Patent Document 2 describes a black inkjet ink used in a disperse dye ink for textile printing, characterized in that it contains a water-soluble organic solvent containing glycol ether and first to fourth disperse dyes that have a maximum absorption wavelength in a specific wavelength range in the ultraviolet-visible spectral absorption of a solution dissolved in acetone. Although the document mentions an ink that is directly applied to pretreated polyester fibers in a direct printing method, it does not go so far as to examine the technology related to dyes with sublimation properties that can be used in a sublimation transfer method, and does not disclose the uniformity of dyeing or dyeing performance in high-concentration dyeing.

WO2005/121263 Patent No. 6191234

However, it was difficult to obtain a black ink that had high color development while maintaining the black hue and suppressed hue changes due to the influence of color rendering, because the types of dyes and their blending ratios that could satisfy these requirements were limited.

The present invention aims to provide a coloring liquid that, when used to dye hydrophobic fibers, can produce dyed products with high color development that maintains the black hue and that have little change in hue due to the influence of color rendering properties.

(Relationship with color rendering properties)
In order to prevent the hue from changing even under a light source that has little light on the long wavelength side, such as a fluorescent lamp, it is preferable to combine dyes that have absorption on the long wavelength side as well. In order to achieve this objective, it has been found that it is preferable to include a water-insoluble colorant D, which has a maximum absorption wavelength in the wavelength range of 640 nm or longer and 700 nm or shorter in the ultraviolet-visible spectral absorption of a DMF solution, as a disperse dye.

(Relationship with color development)
Water-insoluble colorant D, which has a maximum absorption wavelength in the wavelength region longer than 640 nm and 700 nm or shorter in the ultraviolet-visible spectral absorption of a DMF solution, often has partial absorption in the region longer than the 400 nm to 700 nm range generally considered to be visible light, and tends to cause low color development of printed matter when viewed visually. It has been found that in order to maintain black color development, the ratio of the above water-insoluble colorant D, calculated by the formula (D)/(A+C), needs to be less than 0.8, where (A+C) is the total content of water-insoluble colorant A and water-insoluble colorant C.

As a result of intensive research conducted by the inventors to solve the above-mentioned problems, the inventors have discovered water-insoluble colorant A having a maximum absorption wavelength in the wavelength region of 410 nm to 450 nm in the ultraviolet-visible spectral absorption of a DMF solution, water-insoluble colorant B having a maximum absorption wavelength in the wavelength region longer than 450 nm and shorter than 470 nm in the ultraviolet-visible spectral absorption of a DMF solution, water-insoluble colorant C having a maximum absorption wavelength in the wavelength region of 590 nm to 640 nm in the ultraviolet-visible spectral absorption of a DMF solution, In a coloring liquid containing a water-insoluble colorant D having a maximum absorption wavelength in the wavelength region longer than 640 nm and shorter than 700 nm in the ultraviolet-visible spectral absorption of the solution, the content of the water-insoluble colorant D in the coloring liquid is (D) and the total content of the water-insoluble colorant A and the water-insoluble colorant C is (A+C), the value calculated by the formula (D)/(A+C) is less than 0.8. It has been found that this coloring liquid solves the above problems, and the present invention has been completed.

That is, the present invention relates to the following 1) to 11).
1)
A colored liquid containing a water-insoluble colorant A having a maximum absorption wavelength in the wavelength region of 410 nm to 450 nm in the ultraviolet-visible spectral absorption of a DMF solution, a water-insoluble colorant B having a maximum absorption wavelength in the wavelength region of longer than 450 nm and shorter than 470 nm in the ultraviolet-visible spectral absorption of a DMF solution, a water-insoluble colorant C having a maximum absorption wavelength in the wavelength region of 590 nm to 640 nm in the ultraviolet-visible spectral absorption of a DMF solution, and a water-insoluble colorant D having a maximum absorption wavelength in the wavelength region of longer than 640 nm and shorter than 700 nm in the ultraviolet-visible spectral absorption of a DMF solution, wherein the content of the water-insoluble colorant D in the colored liquid is (D) and the total content of the water-insoluble colorant A and the water-insoluble colorant C is (A+C), the value calculated by the formula (D)/(A+C) is less than 0.8.
2)
The coloring liquid according to 1), further comprising a dispersant, a surfactant and water.
3)
The coloring liquid according to 1) or 2), wherein the a ^* value in the CIE color space is within a range of −25 to −10 when the absorbance at the maximum absorption wavelength of the water-insoluble colorant A in a DMF solution is taken as 1, and the a ^* value in the CIE color space is within a range of 15 to 35 when the absorbance at the maximum absorption wavelength of the water-insoluble colorant B in a DMF solution is taken as 1.
4)
The colored liquid according to any one of 1) to 3), wherein the value calculated by the formula (D)/(A+C) is 0.03 or more and less than 0.8.
5)
The colored liquid according to any one of 2) 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 coloring liquid according to 5), wherein the formalin condensate of an aromatic sulfonic acid or a salt thereof includes a formalin condensate of a creosote oil sulfonic acid or a salt thereof.
7)
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 recording medium obtained by using the coloring liquid according to any one of 1) to 8).
10)
9) The recording medium according to 9), wherein the recording medium is made of hydrophobic fibers.
11)
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) onto an intermediate recording medium to obtain a recorded image; and a transfer step of contacting a hydrophobic fiber with the coloring liquid-deposited surface of the intermediate recording medium and heat-treating the hydrophobic fiber to transfer the recorded image to the hydrophobic fiber.

The present invention makes it possible to produce dyed products with little change in hue due to the influence of color rendering properties in sublimation transfer dyeing using inkjet printing, and to provide a coloring liquid that has high sublimation transfer efficiency and can produce dyed products with high concentration, a recording medium to which the coloring liquid is attached, and a printing method for hydrophobic fibers using the coloring liquid.

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

The coloring liquid is a water-insoluble colorant A having a maximum absorption wavelength in the wavelength region of 410 nm to 450 nm in the ultraviolet-visible spectral absorption of a DMF solution, a water-insoluble colorant B having a maximum absorption wavelength in the wavelength region of longer than 450 nm and shorter than 470 nm in the ultraviolet-visible spectral absorption of a DMF solution, and a water-insoluble colorant B having a maximum absorption wavelength in the wavelength region of 590 nm to 640 nm in the ultraviolet-visible spectral absorption of a DMF solution. C. A colored liquid containing a water-insoluble colorant D, which has a maximum absorption wavelength in a wavelength region longer than 640 nm and shorter than 700 nm in an ultraviolet-visible spectral absorption of a DMF solution, wherein the content of the water-insoluble colorant D in the colored liquid is (D) and the total content of the water-insoluble colorant A and the water-insoluble colorant C is (A+C), the value calculated by the formula (D)/(A+C) is less than 0.8.
Hereinafter, each component contained in the coloring liquid according to this embodiment will be described.

[Water-insoluble colorants A to D]
The water-insoluble colorants A to D according to the present invention include pigments, disperse dyes, oil-soluble dyes, etc., with disperse dyes and oil-soluble dyes being preferred.

[Water-insoluble colorant A]
The water-insoluble colorant A is not particularly limited as long as it is a colorant having a maximum absorption wavelength in the wavelength range of 410 nm to 450 nm in the ultraviolet-visible spectral absorption of a DMF solution. Examples of the water-insoluble colorant A include, for example, C.I. Disperse Yellow 5, 42, 49, 50, 51, 54, 58, 60, 64, 71, 82, 83, 88, 93, 99, 100, 103, 114, 119, 126, 149, 160, 162, 164, 165, 180, 182, 183, 184:1, 186, 192, 198, 202, 204, 211, 215, 216, 218, 224, 226, 231, 232, 234, C.I. Solvent Yellow 16, 29, 33, 44, 56, 77, 79, 93, 98, 103, 104, 105, 112, 116, 117, 122, 126, 144, 145, 157, 160, 160:1, 163, 200, C.I. Solvent Green 5, etc. are mentioned, preferably C.I. Disperse Yellow 54, 82, 232, more preferably C.I. Disperse Yellow 54. In addition, the water-insoluble colorant A may be used alone or in combination of multiple types.

[Water-insoluble colorant B]
The water-insoluble colorant B is not particularly limited as long as it is a colorant having a maximum absorption wavelength in the wavelength region of 450 nm or longer and 470 nm or shorter in the ultraviolet-visible spectral absorption of a DMF solution, and examples of the water-insoluble colorant B include, for example, C.I. Disperse Brown 26 and 27, and C.I. Disperse Brown 27 is preferable. The water-insoluble colorant B may be used alone or in combination of two or more kinds.

[Water-insoluble colorant C]
The water-insoluble colorant C is not particularly limited as long as it is a colorant having a maximum absorption wavelength in the wavelength region of 590 nm to 640 nm in the ultraviolet-visible spectral absorption of a DMF solution, and examples of the water-insoluble colorant C include, for example, C.I. Disperse Blue 19, 26, 27, 54, 56, 64, 72, 73, 81, 77, 128, 148, 149, 153, 158, 165, 165:1, 165:2, 183, 197, 224, 225, 257, 268, 287, 337, 345, 360, C.I. Solvent Blue 35, 36, 78, 111, 112, C.I. Solvent Violet 13, and the like, and preferably C.I. Disperse Blue 72, 360, C.I. Preferred is C.I. Solvent Violet 13, and more preferred is C.I. Disperse Blue 360. The water-insoluble colorant C may be used alone or in combination of two or more kinds.

[Water-insoluble colorant D]
The water-insoluble colorant D is not particularly limited as long as it is a colorant having a maximum absorption wavelength in the wavelength region of 640 nm or longer and 700 nm or shorter in the ultraviolet-visible spectral absorption of a DMF solution, and examples of the water-insoluble colorant D include, for example, C.I. Disperse Blue 58, 60, 87, 108, 143, 181, 185, 198, 288, 334, 354, 359, C.I. Solvent Blue 67, etc., preferably C.I. Disperse Blue 60, 334, 359, and more preferably C.I. Disperse Blue 359. The water-insoluble colorant D may be used alone or in combination of multiple types.

The coloring liquid may further contain other water-insoluble colorants other than the above water-insoluble colorants A to D. The other water-insoluble colorants are not particularly limited as long as they are water-insoluble colorants not included in any of the above water-insoluble colorants A to D, and are selected from disperse dyes, oil-soluble dyes, pigments, etc.

The DMF solutions described in the above items for water-insoluble colorants A to D refer to solutions in which water-insoluble colorants A to D are dissolved or dispersed in DMF (N,N-dimethylformamide) and the concentration is adjusted so that the absorbance at the maximum absorption wavelength in the ultraviolet-visible spectral absorption is 1.

If the content of water-insoluble colorant D in the coloring liquid is (D) and the total content of water-insoluble colorant A and water-insoluble colorant C is (A+C), the value calculated by the formula (D)/(A+C) is less than 0.8, preferably 0.03 or more and less than 0.8, more preferably more than 0.03 and 0.75 or less, particularly preferably 0.05 or more and 0.75 or less, and extremely preferably 0.1 or more and 0.7 or less.

In one preferred embodiment, the a ^* value in the CIE color space is within a range of −25 to −10 when the absorbance at the maximum absorption wavelength of the water-insoluble colorant A in a DMF solution is taken as 1, and the a ^* value in the CIE color space is within a range of 15 to 35 when the absorbance at the maximum absorption wavelength of the water-insoluble colorant B in a DMF solution is taken as 1.

The above water-insoluble colorants A to D and other water-insoluble colorants (hereinafter, these may be collectively referred to simply as colorants) may be in the form of powder or lump dry colorants, wet cakes, or slurries, and may contain a small amount of a dispersant such as a surfactant to suppress aggregation of colorant particles during or after colorant synthesis. Commercially available dyes are available in grades for industrial dyeing, resin coloring, ink, toner, inkjet, etc., and each grade has a different manufacturing method, purity, particle size, etc. Smaller particles are preferred as colorants to suppress aggregation after pulverization, and it is also preferred to use colorants with as few impurities as possible due to their effect on dispersion stability and ink ejection accuracy.

The coloring liquid may further contain a dispersant, a surfactant, and water.

As the dispersant, for example, styrene-(meth)acrylic copolymer, formalin condensate of aromatic sulfonic acid or its salt, polyoxyethylene arylphenyl ether, polyoxyethylene phenyl ether sulfate, polyoxyethylene naphthyl ether, etc. can be used. The styrene-(meth)acrylic copolymer is a copolymer of a styrene-based monomer and a (meth)acrylic monomer. 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, (α-methyl)styrene-methacrylic acid copolymer, (α-methyl)styrene-methacrylic acid-acrylic acid ester copolymer, (α-methyl)styrene-(anhydride) maleic acid copolymer, acrylic acid ester-(anhydride) maleic acid copolymer, (α-methyl)styrene-acrylic acid ester-(anhydride) maleic acid copolymer, acrylic acid ester-allylsulfonic acid ester copolymer, acrylic acid ester-styrenesulfonic 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 copolymer; and the like. Among these, the compound containing an aromatic hydrocarbon group is preferably styrene. In this specification, (α-methyl)styrene is used to mean α-methylstyrene and styrene. In the coloring liquid, the dispersant preferably contains at least one dispersant selected from the group consisting of styrene-(meth)acrylic copolymer, formalin condensate of aromatic sulfonic acid or its salt, polyoxyethylene arylphenyl ether, polyoxyethylene phenyl ether sulfate, and polyoxyethylene naphthyl ether. The content of the dispersant in the coloring liquid 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, but are not limited to, Joncryl ^RTM 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). In this specification, the superscript RTM 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 styrene-acrylic acid copolymer is measured by GPC (gel permeation chromatography). 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 small, the solubility of the resin in water is poor, and especially when the water-insoluble colorant is a dispersible dye, the dispersion stabilization power tends to be poor. If the acid value is too large, the affinity with the aqueous medium becomes strong, and the image after printing tends to bleed easily, which is not preferable. The acid value of the resin represents the number of milligrams of KOH required to neutralize 1 g of the resin, and is measured according to JIS-K3054. 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 that are preferred dispersants in the coloring 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 above colored liquid can be prepared by using two or more types of styrene-acrylic copolymers when dispersing or dissolving the above water-insoluble colorants A to D and other water-insoluble colorants.

The above water-insoluble colorants A to D and other water-insoluble colorants can be dispersed, for example, by the following method. A styrene-acrylic copolymer is added to a water-soluble organic solvent, and the temperature is raised to 90-120°C to prepare a styrene-acrylic copolymer solution. An alkaline compound and water are added to the solution, and the temperature is lowered to prepare an emulsified (emulsion or microemulsion) solution. The prepared emulsion solution and the colorant are mixed and dispersed.

The above-mentioned formalin condensate of aromatic sulfonic acid or its salt is an anionic surfactant obtained by a condensation reaction of aromatic sulfonic acid and formalin. Examples of the "salt" include sodium salt, potassium salt, lithium salt, and the like. The above-mentioned 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, when the term "formalin condensate of sulfonic acid" is used, it also means "a salt thereof or a mixture thereof"). For example, 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, lignin sulfonic acid, and the like can be mentioned. Among these, the formalin condensates of creosote oil sulfonic acid, β-naphthalene sulfonic acid, lignin sulfonic acid, and methylnaphthalene sulfonic acid are preferred. These are available as commercial products under various trade names. Examples of such products 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, Labelin AN series, and Labelin W series are preferred, Demol N and Labelin W are more preferred, and Labelin W is even more preferred. Examples of lignin sulfonic acid 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 repetitions of the polyoxyethylene group in the polyoxyethylene aryl phenyl ether is preferably 1 to 30, and more preferably 15 to 30. When the number of repetitions is 1 or more, the compatibility with aqueous solvents and the like tends to be excellent. Also, when the number of repetitions is 30 or less, the viscosity tends not to be too high. Among the 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, Paionin D-6320 (all manufactured by Takemoto Oil Co., Ltd.); TS-1500, TS-2000, TS-2600, SM-174N (all manufactured by Toho Chemical Industry Co., Ltd.); Emulgen A-60, Emulgen A-90, Emulgen A-500 (all manufactured by Kao Corporation); and the like.

The polyoxyethylene aryl phenyl ether sulfate may be the polyoxyethylene styryl phenyl ether sulfate described above. Among the polyoxyethylene aryl phenyl ether sulfates described above, polyoxyethylene styryl phenyl ether sulfate is preferred. Examples of commercially available polyoxyethylene styryl phenyl ether sulfate include SM-57 and SM-210 (both manufactured by Toho Chemical Industry Co., Ltd.).

Commercially available examples of the polyoxyethylene naphthyl ether include the Noigen EN series (manufactured by Daiichi 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 above, the coloring liquid according to this embodiment 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, oxyethylene oxypropylene block polymers, and substituted derivatives thereof. As alkylene oxide adducts of cholestanols, C2-C4 alkylene oxide adducts of cholestanols are preferred, and ethylene oxide adducts are more preferred. In this specification, "cholestanols" is used to mean 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 mole of cholestanols is preferably about 10 to 50 moles, and the HLB is preferably about 13 to 20.

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

Examples of the above surfactants include known surfactants such as anionic, cationic, nonionic, and silicone surfactants. Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and their salts, N-acyl methyl taurine salts, alkyl sulfate polyoxyalkyl ether sulfates, alkyl sulfate polyoxyethylene alkyl ether phosphates, rosin acid soap, castor oil sulfate esters, lauryl alcohol sulfate esters, alkyl phenol phosphates, alkyl phosphates, alkylaryl sulfonates, diethyl sulfosuccinates, diethylhexyl cyrsulfosuccinates, and dioctyl sulfosuccinates. Specific examples of commercially available products include, for example, Hitenol LA-10, LA-12, LA-16, Neo Hitenol ECL-30S, and ECL-45, all manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Examples of cationic surfactants include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives. Examples of amphoteric surfactants include lauryl dimethylaminoacetate betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, coconut oil fatty acid amidopropyl dimethylaminoacetate 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; trade names Surfynol 104, 105, 82, 465, and Olfin STG, manufactured by Nissin Chemical Industry Co., Ltd.; and polyglycol ether-based surfactants (for example, Tergitol manufactured by SIGMA-ALDRICH Co., Ltd.). 15-S-7, etc.); etc.

Examples of the silicone surfactant include polyether-modified siloxane and polyether-modified polydimethylsiloxane. Specific examples of commercially available products include BYK-347 (polyether-modified siloxane), BYK-345, and BYK-348 (polyether-modified polydimethylsiloxane), all manufactured by BYK-Chemie. Examples of fluorine-based surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups on the side chains. 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), etc.

The water is preferably ion-exchanged water, distilled water, or other water with few impurities. The coloring liquid may be subjected to precision filtration using a membrane filter or the like. When using the coloring liquid as an inkjet textile printing ink, it is preferable to perform precision filtration to prevent nozzle clogging. The pore size of the filter used for precision filtration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

It is preferable that the coloring liquid further contains a phytosterol-based 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, "phytosterols" is used to mean both "phytosterol" and "hydrogenated phytosterol". For example, examples of 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 (same, ethylene oxide adduct of hydrogenated phytosterols). Commercially available alkylene oxide adducts of cholestanols include NIKKOL DHC-30 (manufactured by Nikko Chemicals Co., Ltd., ethylene oxide adduct of cholestanol), with NIKKOL BPS-30 being preferred.

The coloring liquid may further contain additives.

Examples of the additives include 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, and antioxidants.

Examples of the water-soluble organic solvent include glycol-based solvents, polyhydric alcohols, pyrrolidones, etc. Examples of glycol-based solvents include glycerin, polyglycerin (#310, #750, #800), diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, undecaglycerin, dodecaglycerin, tridecaglycerin, tetradecaglycerin, and other compounds, and mixtures thereof. Examples of polyhydric alcohols include C2-C6 polyhydric alcohols having 2-3 alcoholic hydroxyl groups, and di- or tri-C2-C3 alkylene glycols or poly-C2-C3 alkylene glycols having 4 or more repeating units and a molecular weight of about 20,000 or less, preferably liquid polyalkylene glycols. Specific examples of these 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 and other polyhydric alcohols, 2-pyrrolidone, N-methyl-2-pyrrolidone, and the like, and it is preferable to include at least one of glycerin or diglycerin. For convenience, compounds that dissolve in water and act as wetting agents are also included in the water-soluble organic solvent in the present invention, and examples of such compounds include urea, ethylene urea, and sugars. Considering storage stability, when the colorant is a disperse dye or oil-soluble dye, a solvent in which the solubility is low is preferred, and 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 water-soluble organic solvents in the total mass of the coloring liquid is 5 to 50%, and it is preferable to add 10 to 40%.

Examples of the preservative include organic sulfur, organic nitrogen sulfur, organic halogen, haloarylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzothiazole, isothiazolinone, dithiol, pyridine oxide, nitropropane, organic tin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone, benzyl bromoacetate, inorganic salt, and other 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 antiseptics and fungicides include sodium acetate anhydride, sodium sorbate, or sodium benzoate, and Arch Chemical Company's products under the trade names Proxel ^RTM GXL(S) and Proxel ^RTM XL-2(S).

As the pH adjuster, any substance can be used as long as it can control the pH of the solution to a range of approximately 5 to 11 without adversely affecting the colored liquid being prepared. 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 chelating agent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracildiacetate.

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

Examples of the water-soluble UV absorbers 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, etc.

The viscosity adjuster may be a water-soluble organic solvent or a water-soluble polymer compound, such as polyvinyl alcohol, a cellulose derivative, a polyamine, or a polyimine.

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

The above-mentioned anti-fading agents are used for the purpose of improving the storage stability of images. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Examples of organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of metal complex anti-fading agents include nickel complexes and zinc complexes.

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

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

The coloring liquid may further contain a resin emulsion.

The above resin emulsions include, for example, emulsions formed from acrylic resin, epoxy resin, urethane resin, polyether resin, polyamide resin, unsaturated polyester resin, phenol resin, silicone resin, fluororesin, polyvinyl resin (e.g., vinyl chloride, vinyl 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 types of resin. Furthermore, they may be composite resins in which two or more types of resin form a core/shell structure. Among these resin emulsions, urethane resin is preferred for use in the above coloring liquid.

The above urethane resins are often sold in the form of latex (emulsion), and most of them are emulsions with a solid content of 30 to 60%. Specific examples include Permarin UA-150, 200, 310, 368, 3945, and U-coat UX-320 (all manufactured by Sanyo Chemical Industries, Ltd.), Hydran WLS-201, 210, and HW-312B latex (all manufactured by DIC Corporation), and Superflex 150, 170, and 470 (all manufactured by 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. In addition, if the resin in the urethane resin emulsion has acidic groups, and the emulsion is produced by neutralizing these acidic groups, the SP value of the resin before neutralization is used.

When the urethane resin emulsion has acidic groups such as carboxylic acid, sulfonic acid, or hydroxyl groups, the acidic groups may be converted into an alkali salt. The alkali salt can be made, for example, by the following method. One example is a method in which a urethane resin emulsion having acidic groups is put into water and stirred to prepare an aqueous solution, and an alkaline compound is added to the aqueous solution to prepare a liquid with 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, hydroxides of alkaline earth metals such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide, and triethylamine. Any one of these alkaline compounds may be used alone, or two or more of them may be used in combination.

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

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

Methods for dispersing the coloring liquid include known methods such as stirring and mixing the components constituting the coloring liquid using a sand mill (bead mill), roll mill, ball mill, paint shaker, ultrasonic disperser, high-pressure emulsifier, etc. As an example, when using a sand mill, first, the components and beads as a dispersion medium are charged into the sand mill. As the beads, glass beads, zirconia beads, etc. with a particle diameter of 0.01 to 1 mm can be used. The amount of beads used is preferably 2 to 6 parts by mass per 1 part by mass of the dispersion target. Next, the sand mill is operated to perform a dispersion treatment. The dispersion treatment conditions are preferably approximately 1000 to 2000 rpm and 1 to 20 hours. After the dispersion treatment, the beads are removed by filtration or the like to obtain a 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 A to D and other water-insoluble colorants are each dispersed may be mixed.

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

The prepared coloring liquid and the ink containing the coloring liquid may be subjected to precision filtration using a membrane filter or the like. In particular, when the coloring liquid is used as an ink for inkjet textile printing, it is preferable to perform precision filtration in order to prevent nozzle clogging and the like. The pore size of the filter used for precision filtration is usually 0.1 to 1 μm, and preferably 0.1 to 0.8 μm.

In terms of high-speed ejection response, the above inks preferably have a viscosity at 25°C of typically 3 to 20 mPa·s when measured with an E-type viscometer. Furthermore, the surface tension preferably ranges from typically 20 to 45 mN/m when measured with the plate method. It is preferable to adjust each of these values to an appropriate value, taking into consideration the ejection volume, response speed, and ink droplet flight characteristics of the printer being used.

The present invention also includes ink sets containing the above inks and other inks.
The other inks mentioned above refer to inks having a composition and hue different from those of the above inks, and examples thereof include, but are not limited to, yellow ink, magenta ink, cyan ink, orange ink, violet ink, green ink, turquoise ink, blue ink, etc. Also included are light yellow ink, light magenta ink, light cyan ink, light black ink, etc., which are inks in which the total concentration of the colorant in the ink has been changed (low concentration ink or high concentration ink) compared to the above inks or the other inks mentioned above.

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, 122, 1 24, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184, 184:1, 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, 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.; 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.; etc.

Specific examples of the above oil-soluble dyes include, for example, 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, 160:1, 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.: C.I. 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 may be used alone or in combination.

The present invention also includes recording media obtained using the above coloring liquid or ink containing the coloring liquid.

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, and fabric, particularly hydrophobic fiber, is 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. In addition, blended fibers of these with regenerated fibers such as rayon, and natural fibers such as cotton, silk, and wool are also included in the hydrophobic fibers in this specification. Some of these hydrophobic fibers are known to have an ink-receiving layer (bleed prevention layer), and such hydrophobic fibers are also included. The method of forming the ink-receiving layer is a known technology, and fibers having an ink-receiving layer are also commercially available. There are no particular limitations on the material or structure of the ink-receiving layer, and it can be used appropriately depending on the purpose, etc.

The coloring liquid or the ink containing the coloring liquid can be used in various fields, but is suitable for use as a water-based ink for writing, a water-based printing ink, an information recording ink, textile printing, etc., and is particularly preferably used as an ink for inkjet textile printing.

The present invention also includes a printing method for hydrophobic fibers, which includes a printing step of depositing droplets of the coloring liquid or ink containing the coloring liquid on an intermediate recording medium to obtain a recorded image, and a transfer step of contacting a hydrophobic fiber with the surface of the intermediate recording medium on which the coloring liquid or ink containing the coloring liquid has been deposited, and then subjecting the hydrophobic fiber to a heat treatment to transfer the recorded image to the hydrophobic fiber. The present invention also includes an intermediate recording medium to which the coloring liquid or ink containing the coloring liquid has been deposited.

The above-mentioned hydrophobic fiber printing method is roughly divided into two types. The first method is a method called direct printing or direct printing, which is a hydrophobic fiber printing method that includes at least three steps: step A in which droplets of the above-mentioned coloring liquid or ink containing the coloring liquid are attached to the hydrophobic fiber by an inkjet printer to form image information such as characters and patterns on the hydrophobic fiber; step B in which the sublimation dye in the droplets of the above-mentioned coloring liquid or ink containing the coloring liquid attached in step A is fixed to the fiber by heat; and step C in which the unfixed sublimation dye remaining in the fiber is washed off. Step B is generally performed by known steaming or baking. Examples of the steaming include a method of treating hydrophobic fibers with a sublimation dye (also called wet heat fixation) by using a high-temperature steamer at 170 to 180°C for about 10 minutes, and a method of treating hydrophobic fibers with a high-pressure steamer at 120 to 130°C for about 20 minutes. Examples of the baking (thermosol) include a method of treating hydrophobic fibers with a sublimation dye (also called dry heat fixation) by using a method of treating hydrophobic fibers at 190 to 210°C for about 60 to 120 seconds. Step C is a step of washing the obtained fibers with hot water and, if necessary, water. The hot 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., and is a hydrophobic fiber printing method in which droplets of the coloring liquid or the ink containing the coloring liquid or the ink set are attached to an intermediate recording medium by an inkjet printer to obtain a recorded image such as characters and patterns, and then the coloring liquid or the ink containing the coloring liquid is brought into contact with a hydrophobic fiber on the surface of the intermediate recording medium on which the droplets of the coloring liquid or the ink containing the coloring liquid are attached, and the recorded image such as characters and patterns recorded on the intermediate recording medium is transferred to the hydrophobic fiber by heat treatment. As the intermediate recording medium, it is preferable that the sublimable dye in the coloring liquid or the ink containing the coloring liquid attached to 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. One example of such an intermediate recording medium is paper on the surface of which a coloring liquid receiving layer is formed of inorganic fine particles such as silica, and dedicated paper for inkjet printing can be used. As the heat treatment when transferring the recorded image from the intermediate recording medium to the hydrophobic fiber, a dry heat treatment at about 190 to 200°C is usually used.

In the above-mentioned dyeing method by immersion dyeing, the hydrophobic fiber is immersed in the coloring solution of the present invention and dyed under pressure, preferably at 105°C or higher, more preferably at 110 to 140°C, for preferably 30 minutes to 1 hour. It is particularly preferable to dye at 120 to 130°C for 30 to 45 minutes. It is also possible to dye in the presence of a carrier such as o-phenylphenol or trichlorobenzene, for example, in boiling water. Alternatively, it is also possible to dye using the so-called thermosol method, in which the coloring solution of the present invention is padded onto the hydrophobic fiber and then dry heat treatment is performed at 150 to 230°C for 30 to 1 minute.

The above-mentioned printing method may further include a fiber pretreatment step for the purpose of preventing bleeding and the like. The pretreatment step includes a step of applying an aqueous solution containing at least one type of paste, an alkaline substance, a reduction inhibitor, and a hydrotropic agent to the fiber before the coloring liquid or the ink containing the coloring liquid is applied. In the pretreatment step, it is preferable to use an aqueous solution of a pretreatment agent containing a paste, an alkaline substance, a reduction inhibitor, and a hydrotropic agent as a pretreatment liquid, and impregnate the fiber with the pretreatment liquid. Examples of the paste include natural gums such as guar and locust bean, starches, sodium alginate, seaweed such as funori, plant skins such as pectinic acid, cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose, processed starches such as carboxymethyl starch, and synthetic pastes such as polyvinyl alcohol and polyacrylic esters. Sodium alginate is preferable.

Examples of the alkaline substance include alkali metal salts of inorganic or organic acids, salts of alkaline earth metals, and compounds that liberate alkali when heated. Inorganic or organic alkali metal hydroxides and alkali metal salts are preferred, and sodium compounds and potassium compounds are included. Specific examples include alkali metal hydroxides such as sodium hydroxide and calcium hydroxide, alkali metal salts of inorganic compounds such as sodium carbonate, sodium hydrogen carbonate, 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 hydrogen carbonate is preferred. The reduction inhibitor is preferably sodium meta-nitrobenzenesulfonate. The hydrotropic agent is, for example, urea, dimethyl urea, and other ureas, and urea is preferred. The sizing agent, alkaline substance, reduction inhibitor, and hydrotropic agent may all be used as 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, 0.5-5% starch, 0.5-5% sodium bicarbonate, 0-5% sodium metanitrobenzenesulfonate, 1-20% urea, and the remainder water, all based on mass. The pretreatment agent can be applied to cellulosic fibers by padding, for example. The squeezing rate of padding is preferably about 40-90%, and more preferably about 60-80%.

The coloring liquid or ink containing the coloring liquid of the present invention has excellent storage stability without solid precipitation, changes in physical properties, or color changes after long-term storage. In addition, the initial filling property into the inkjet printer head is good, and the continuous printing stability is also good. Furthermore, it is possible to obtain a clear image without bleeding of the image on the paper after printing. In addition to these, the dyed material dyed with the coloring liquid of the present invention or the ink containing the coloring liquid has a high dyeing concentration, excellent uniformity, and a high-quality black hue. Furthermore, full-color inkjet printing with excellent fastness and excellent storage properties is possible. Thus, the coloring liquid or ink containing the coloring liquid of the present invention is particularly suitable for inkjet printing ink because it has extremely excellent ejection stability. In particular, the value of the dyeing concentration is high, at a color development concentration of 340 or more represented by Sigma K/S in the dyeing concentration evaluation below, resulting in a black color with extremely excellent color rendering properties, and a better black printed material with excellent uniformity can be obtained, so that the coloring liquid or the ink containing the coloring liquid is more excellent.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified, "parts" means parts by mass, and "%" means mass%. Note that the inks in each example are all included in the coloring liquid. In the following text and tables, Example 8 shall be read as Reference Example 1.

The colorants used in the examples and comparative examples corresponding to water-insoluble colorants A to D were dissolved or dispersed in DMF, and the concentration of the solution was adjusted so that the absorbance at the maximum absorption wavelength in the ultraviolet-visible spectral absorption was 1. The results are shown in Table 1.

[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]
A mixture of water-insoluble colorant Kayaset Yellow AG (manufactured by Nippon Kayaku Co., Ltd., C.I. Disperse Yellow 54, a ^* value -20) (10 parts), Labellin W-40 (creosote oil sodium sulfonate formalin polycondensate aqueous solution, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) (15 parts), NIKKOL BPS-30 (0.8 parts), Surfynol 104PG50 (Surfynol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted to a concentration of 50% with propylene glycol) (0.2 parts), Proxel GXL (S) (manufactured by Lonza) (0.1 parts), and ion-exchanged water (73.9 parts) was added with 0.2 mm diameter glass beads, and the mixture was subjected to a dispersion treatment for about 15 hours under cooling with a sand mill. The resulting 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 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 water-insoluble colorant was changed to commercially available C.I. Disperse Orange 25.
[Preparation Example 4: Preparation of Aqueous Dispersion 3]
An aqueous dispersion 3 was obtained in the same manner as in Preparation Example 2, except that the water-insoluble colorant was changed to commercially available C.I. Solvent Orange 60.
[Preparation Example 5: Preparation of Aqueous Dispersion 4]
An aqueous dispersion 4 was obtained in the same manner as in Preparation Example 2, except that the water-insoluble colorant was changed to commercially available C.I. Disperse Brown 27 (a ^* value: 30).
[Preparation Example 6: Preparation of Aqueous Dispersion 5]
An aqueous dispersion 5 was obtained in the same manner as in Preparation Example 2, except that the water-insoluble colorant was changed to commercially available C.I. Disperse Blue 359.
[Preparation Example 7: Preparation of Aqueous Dispersion 6]
An aqueous dispersion 6 was obtained in the same manner as in Preparation Example 2, except that the water-insoluble colorant was changed to commercially available C.I. Disperse Blue 360.
Preparation Example 8: Preparation of Aqueous Dispersion 7
A mixture of Kayaset Yellow AG (manufactured by Nippon Kayaku Co., Ltd., C.I. Disperse Yellow 54) (10 parts) as a water-insoluble 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 concentration of 50% with propylene glycol) (0.2 parts), Proxel GXL(S) (manufactured by Lonza) (0.1 parts), and ion-exchanged water (59.7 parts) was mixed with 0.2 mm diameter glass beads, and dispersed in a sand mill for about 15 hours under cooling. 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 7.
Preparation Example 9: Preparation of Aqueous Dispersion 8
An aqueous dispersion 8 was obtained in the same manner as in Preparation Example 8, except that the water-insoluble colorant was changed to commercially available C.I. Disperse Brown 27.
Preparation Example 10: Preparation of Aqueous Dispersion 9
An aqueous dispersion 9 was obtained in the same manner as in Preparation Example 8, except that the water-insoluble colorant was changed to commercially available C.I. Disperse Blue 359.
Preparation Example 11: Preparation of Aqueous Dispersion 10
An aqueous dispersion 10 was obtained in the same manner as in Preparation Example 8, except that the water-insoluble colorant was changed to commercially available C.I. Disperse Blue 360.
Preparation Example 12: Preparation of Aqueous Dispersion 11
A mixture of water-insoluble colorants, such as Kayaset Yellow AG (manufactured by Nippon Kayaku Co., Ltd., C.I. Disperse Yellow 54) (10 parts), 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 concentration of 50% 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 subjected to a dispersion treatment for about 15 hours under cooling with a sand mill. The obtained liquid was filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC Co., Ltd., filter pore size: 0.5 μm) to obtain an aqueous dispersion 11.
Preparation Example 13: Preparation of Aqueous Dispersion 12
An aqueous dispersion 12 was obtained in the same manner as in Preparation Example 12, except that the water-insoluble colorant was changed to commercially available C.I. Disperse Brown 27.
Preparation Example 14: Preparation of Aqueous Dispersion 13
An aqueous dispersion 13 was obtained in the same manner as in Preparation Example 12, except that the water-insoluble colorant was changed to commercially available C.I. Disperse Blue 359.
[Preparation Example 15: Preparation of Aqueous Dispersion 14]
An aqueous dispersion 14 was obtained in the same manner as in Preparation Example 12, except that the water-insoluble colorant was changed to commercially available C.I. Disperse Blue 360.
Preparation Example 16: Preparation of Example Inks and Comparative Example Inks
The aqueous dispersions 1 to 14 obtained above were mixed with the components shown in Table 2 below, stirred for 30 minutes, and then filtered through glass fiber filter paper GC-50 (manufactured by Advantec Corporation, filter pore size: 0.5 μm) to prepare each of the inks of Examples 1 to 12 and Comparative Example 1. In the table, the numerical value for each component indicates the number of parts added.

The abbreviations in Table 2 respectively indicate the following.
Surfynol 465: nonionic surfactant manufactured by Nissin Chemical Industry Co., Ltd. TEA80: 80% aqueous solution of triethanolamine

If the content of water-insoluble colorant D in Examples 1 to 12 and Comparative Example 1 is (D), and the total content of water-insoluble colorant A and water-insoluble colorant C is (A+C), the values calculated by the formula (D)/(A+C) are as shown in Table 2.

The following evaluation tests were carried out using each of the inks prepared as described above. The results are shown in Table 3 below.

[Intermediate recording medium printed with ink and sublimation transfer printing using the same]
Each of the prepared inks was filled into an inkjet printer (product name PX-504A, manufactured by EPSON CORPORATION), and a monochrome solid image was printed at 100% duty and 40% duty using TRANSJET EcoII 8385 (95 g/m2) as an intermediate recording medium 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 x 30 seconds using a tabletop automatic flat press machine (AF-65TEN, manufactured by Asahi Textile Machinery Co., Ltd.) to obtain dyed products dyed by the sublimation transfer dyeing method. The following evaluations were performed on each of the obtained dyed products.

[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. The color measurement was performed under conditions of D65 light source, viewing angle 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, and 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 means a higher color density and higher quality. Evaluation was performed according to the following evaluation criteria.
[Evaluation criteria]
S: Sigma K/S value is 350 or higher.
A: Sigma K/S value is 345 or greater but less than 350.
B: Sigma K/S value is 340 or more and less than 345.
C: Sigma K/S value is 335 or more and less than 340.
D: Sigma K/S value less than 335.
[Color rendering evaluation]
The hues L ^* , a ^* , and b ^* of the dyed portions of the obtained dyed products at 40% duty were measured using a spectrophotometer "Ci62 (manufactured by X-rite)". The colorimetry was performed using a viewing angle of 2° and status T conditions, and the L ^* , a ^* , and b ^* values for the D65 light source and the A light source were obtained. The color difference ΔE _D65-A between the D65 light source and the A light source was calculated from the obtained L ^* , a ^* , and b ^* values for each light source using the following formula (Formula 3).

△E _D65-A = [(L ^* _D65 - L ^* _A ) ² + (a ^* _D65 - a ^* _A ) ² + (b ^* _D65 - b ^* _A ) ² ] ^0.5 (Equation 3)

The abbreviations in the above formulae stand for the following:
L ^* _D65 : L ^* value under D65 light source L ^* _A : L ^* value under A light source a ^* _D65 : a ^* value under D65 light source a ^* _A : a ^* value under A light source b ^* _D65 : b ^* value under D65 light source b ^* _A : b ^* value under A light source

The smaller the value of ΔE _D65-A calculated by the above formula 3, the more suppressed the hue change due to the influence of color rendering properties is, and the higher the quality is. Evaluation was performed according to the following evaluation criteria.
[Evaluation criteria]
S: Color difference ΔE _D65-A value is less than 1.8.
A: Color difference ΔE _D65-A value is 1.8 or more and less than 2.0.
B: The color difference ΔE _D65-A value is 2.0 or more and less than 2.2.
C: Color difference ΔE _D65-A value is 2.2 or more and less than 2.4.
D: Color difference ΔE _D65-A value is 2.4 or more.

As is clear from the results in Table 3, the inks prepared in Examples 1 to 12 all exhibited excellent performance in suppressing hue changes due to the influence of color rendering properties, and also showed high color development, compared to the ink in Comparative Example 1.

The coloring liquid of the present invention is extremely useful because it can suppress hue changes caused by color rendering properties, can produce dyed products with excellent color development, and can maintain the printability required for various textile printing inks, especially inkjet textile printing inks.

Claims (9)

A coloring solution containing C.I. Disperse Yellow 54, C.I. Disperse Brown 27, C.I. Disperse Blue 360, and C.I. Disperse Blue 359, in which the content of C.I. Disperse Blue 359 in the coloring solution is (D) and the total content of C.I. Disperse Yellow 54 and C.I. Disperse Blue 360 is (A+C), the value calculated by the formula (D)/(A+C) is 0.1 or more and 0.7 or less. The coloring liquid according to claim 1, further comprising a dispersant, a surfactant, and water. 3. The colored liquid according to claim 2, wherein the dispersant comprises 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 liquid according to claim 3, wherein the formalin condensate of aromatic sulfonic acid or its salt includes a formalin condensate of creosote oil sulfonic acid or its salt. The coloring liquid according to claim 3 or 4, 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 5, further comprising a phytosterol compound. A recording medium obtained using the coloring liquid according to any one of claims 1 to 6. The recording medium according to claim 7, wherein the recording medium is made of polyester fiber. A method for printing hydrophobic fibers, comprising a printing step of depositing droplets of the coloring liquid according to any one of claims 1 to 6 on an intermediate recording medium to obtain a recorded image, and a transfer step of contacting a hydrophobic fiber with the surface of the intermediate recording medium on which the coloring liquid has been deposited, and then subjecting the hydrophobic fiber to a heat treatment to transfer the recorded image to the hydrophobic fiber.