JP2022026915A - Coloring liquid and printing method of fiber - Google Patents

Abstract

To provide a coloring liquid capable of preparing a dyed product excellent in color rendering, capable of obtaining a dyed product of high concentration, and capable of obtaining a high-quality dyed product excellent in level printing and light resistance, in a sublimation transfer dyeing using an inkjet printing.SOLUTION: In the ultraviolet visible spectroscopic absorption of a DMF solution, in a colorant liquid containing: a water insoluble colorant A having a maximum absorption wavelength in the wavelength range of 410 nm to 450 nm; a water insoluble colorant B having a maximum absorption wavelength in a wavelength region of a longer wavelength than 450 nm and wavelength of 470 nm or shorter wavelength than that in a UV visible light absorption of the DMF solution; a water insoluble colorant C having a maximum absorption wavelength in a wavelength region of 590 to 640 nm in the UV visible spectroscopic absorption of the DMF solution; and a water insoluble colorant (D) having a maximum absorption wavelength in a wavelength region of longer wavelength than 640 nm and 700 nm or shorter wavelength than that in the UV visible spectroscopic absorption of the DMF solution, a content of the water insoluble colorant D is set to (D), a total content of the water insoluble colorant A and the water insoluble colorant C is set to (A+C), a value calculated by a formula (D)/(A+C) is smaller than 0.8.SELECTED DRAWING: None

Description

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

In recent years, a recording method for performing plate-free printing by inkjet has been proposed, and inkjet printing is also performed in the printing of fibers 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.

The inkjet ink used is mainly a water-based ink, and a dye dispersion in which a sublimating dye selected from a water-insoluble disperse dye group and an oil-soluble dye group is dispersed and stabilized in water using a dispersant. Then, a water-soluble organic solvent as a moisturizing agent (anti-drying agent), a surfactant as a surface tension adjusting agent, and other additives (pH adjusting agent, antiseptic / anti-dyeing agent, defoaming agent, etc.) were used. It is made into ink by optimizing physical properties (physical properties) such as particle size, viscosity, surface tension, and pH (see Patent Document 1).

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 fibers is not required and the cleaning step is omitted.

Since it does not use water, it can be easily dyed, and it has received a lot of attention due to its recent interest in environmental issues regarding wastewater. However, unlike conventional dyeing, there is a problem that the dyeing concentration (color development property) looks low because the cloth does not penetrate into the inside of the cloth and is dyed only on the surface of the non-stained object. Especially for black ink, each company is making various efforts to improve the color development. (Refer to Patent Document 2) In addition, there is a demand for a black ink in which the hue of black is not blurred depending on the sublimation transfer conditions and the sublimation rate is uniform.

When expressing black using a dye having sublimation properties, black is usually expressed by combining a plurality of dyes. This is because a single dye is not sufficient for a black hue and often has a low density, and a good black expression can be achieved by combining a plurality of dyes. However, when the cloth is dyed with a black ink that is a combination of a plurality of dyes having sublimation properties, when the cloth is irradiated with light having a different spectral distribution of the light source depending on the type of the cloth, the black color expressed on the cloth is obtained. The hues sometimes looked different. For example, even if a good color can be expressed under illumination with a small amount of long-wavelength light such as a fluorescent lamp, it looks reddish under sunlight with a large amount of long-wavelength light, and vice versa. Even though it was able to express good colors underneath, it sometimes looked bluish under fluorescent lights. As described above, the characteristic of the illumination light source on the appearance of the color of an object is generally called "color rendering property", and black ink with little change in hue due to the influence of this color rendering property has been required.

On the other hand, in the method of printing hydrophobic fibers in the sublimation transfer method, the sublimation transfer ink is applied (printed) to an intermediate recording medium (dedicated transfer paper, etc.) by an inkjet printer, and the ink is applied (printed) on the intermediate recording medium. A sublimation dye is transferred to the object to be dyed by a heat-bonding method using a heat-bonding roller, a heat-pressing machine, or the like on a superposed object (polyester fiber or the like) to be dyed. In commercial printing, inkjet printing is becoming faster, and inkjet inks are also required to be designed to support high speed. Further, as an intermediate recording medium for sublimation transfer ink, an ink receiving layer is formed on the surface of inorganic fine particles such as silica, and a special paper for inkjet having a relatively large basis weight so that a large amount of ink can be applied. However, in recent years, transfer paper having a smaller basis weight and transfer paper having a smaller ink receiving layer have been used, and high transfer efficiency and high dyeing density are strongly demanded with a small amount of ink. In addition, there is a demand for black ink in which the hue of black is not blurred depending on the sublimation transfer conditions, the sublimation speed is uniform, and the hue is less blurred due to the influence of color rendering properties. Patent Document 2 describes black ink for inkjet used as a disperse dye ink for printing, which is maximal in a specific wavelength range in ultraviolet-visible spectral absorption of a water-soluble organic solvent containing glycol ether and a solution dissolved in acetone. A black ink for inkjet characterized by containing the first to fourth disperse dyes having an absorption wavelength is described, but the ink directly applied to the pretreated polyester fiber in the direct printing method is mentioned. No technical studies have been made on dyes having sublimation properties that can be used in the sublimation transfer method, and the leveling property and dyeing performance in high-concentration dyeing have not been disclosed.

WO2005 / 121263 Japanese Patent No. 6191234

However, it is difficult to obtain black ink that has high color development and suppresses hue changes due to the influence of color rendering while maintaining the hue of black, because the dye types and blending ratios that satisfy them are limited. Met.

INDUSTRIAL APPLICABILITY The present invention provides a colored liquid capable of obtaining a dyed product having a high hue while maintaining a black hue and having a small hue change due to the influence of color rendering properties in the dyeing of hydrophobic fibers. Is the purpose.

(Relationship with color rendering)
In order to prevent the hue from changing even under a light source having a small amount of light on the long wavelength side such as a fluorescent lamp, it is preferable to have absorption on the long wavelength side as a combination of dyes. In order to achieve this task, a water-insoluble colorant D having a wavelength longer than 640 nm in ultraviolet-visible spectroscopic absorption of a DMF solution and a maximum absorption wavelength in a wavelength range of 700 nm or shorter is included as a dispersion dye. Was found to be preferable.

(Relationship with color development)
The water-insoluble colorant D having a wavelength longer than 640 nm and a maximum absorption wavelength in the wavelength range of 700 nm or shorter in the ultraviolet-visible spectroscopic absorption of the DMF solution has a wavelength of 400 nm to 700 nm, which is generally regarded as visible light. Many of them have partial absorption even in the wavelength region longer than the range, and the color development property of the printed matter tends to be low when viewed visually. In order to maintain the color-developing property of black, the ratio of the water-insoluble colorant D is the formula (D) when the total content of the water-insoluble colorant A and the water-insoluble colorant C is (A + C). ) / (A + C) was found to need to be less than 0.8.

As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the water-insoluble colorants A and DMF solutions having a maximum absorption wavelength in the wavelength range of 410 nm to 450 nm in the ultraviolet-visible spectral absorption of the DMF solution. Water-insoluble colorant B, which has a maximum absorption wavelength in the wavelength range of 470 nm or shorter and a wavelength longer than 450 nm in ultraviolet-visible spectral absorption, and a maximum in the wavelength range of 590 nm to 640 nm in ultraviolet-visible spectral absorption of DMF solution. Coloring containing a water-insoluble colorant C having an absorption wavelength and a water-insoluble colorant D having a maximum absorption wavelength in the wavelength range of 700 nm or shorter and having a wavelength longer than 640 nm in ultraviolet-visible spectral absorption of the DMF solution. In the liquid, when 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 formula (D) is used. ) / (A + C), the coloring liquid having a value of less than 0.8 has been found to solve the above-mentioned problems, and the present invention has been completed.

That is, the present invention relates to the following 1) to 11).
1)
Water-insoluble colorant A having a maximum absorption wavelength in the wavelength range of 410 nm to 450 nm in the ultraviolet visible spectral absorption of the DMF solution, a wavelength longer than 450 nm and a wavelength of 470 nm or shorter in the ultraviolet visible spectral absorption of the DMF solution. Water-insoluble colorant B having a maximum absorption wavelength in the region, water-insoluble colorant C having a maximum absorption wavelength in the wavelength range of 590 nm to 640 nm in the ultraviolet-visible spectral absorption of the DMF solution, longer than 640 nm in the ultraviolet-visible spectral absorption of the DMF solution. In a coloring liquid containing a water-insoluble coloring agent D having a maximum absorption wavelength in a wavelength range of 700 nm or shorter, the content of the water-insoluble coloring agent D in the coloring liquid is (D). , When 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 containing a dispersant, a surfactant and water.
3)
When the absorbance of the maximum absorption wavelength of the water-insoluble colorant A in the DMF solution is 1, the a ^* value of the CIE color space is in the range of -25 to -10, and the water-insoluble colorant B is used. The colorant according to 1) or 2), wherein the a ^* value of the CIE color space is in the range of 15 to 35 when the absorbance of the maximum absorption wavelength in the DMF solution is 1.
4)
The coloring liquid according to any one of 1) to 3), wherein the value calculated by the above formula (D) / (A + C) is 0.03 or more and less than 0.8.
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 any one of 2) 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 recording medium obtained by using the coloring liquid according to any one of 1) to 8).
10)
The recording medium according to 9), wherein the recording medium is a hydrophobic fiber.
11)
A printing step in which droplets of the coloring liquid according to any one of 1) to 8) are attached to an intermediate recording medium to obtain a recorded image, and hydrophobic fibers are attached to the adhesion surface of the coloring liquid in the intermediate recording medium. A method for printing a hydrophobic fiber, which comprises a transfer step of transferring the recorded image to the hydrophobic fiber by contacting and heat-treating the image.

INDUSTRIAL APPLICABILITY According to the present invention, in sublimation transfer dyeing using inkjet printing, it is possible to produce a dyed product in which the change in hue due to the influence of color rendering is small, the sublimation transfer efficiency is high, and a dyed product having a high concentration can be obtained. It is possible to provide a recording medium to which the coloring liquid is attached and a method for printing hydrophobic fibers using the coloring liquid.

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

The colorant is a water-insoluble colorant A having a maximum absorption wavelength in the wavelength range of 410 nm to 450 nm in the ultraviolet visible spectral absorption of the DMF solution, and has a wavelength longer than 450 nm in the ultraviolet visible spectral absorption of the DMF solution and is 470 nm or its own. Water-insoluble colorant B having a maximum absorption wavelength in a shorter wavelength range, ultraviolet-visible spectroscopy of a water-insoluble colorant C having a maximum absorption wavelength in the wavelength range of 590 nm to 640 nm in ultraviolet-visible spectral absorption of a DMF solution. In a coloring liquid containing a water-insoluble coloring agent D having a wavelength longer than 640 nm in absorption and having a maximum absorption wavelength in a wavelength range of 700 nm or shorter, the content of the water-insoluble coloring agent D in the coloring liquid. When the ratio 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 is a coloring liquid that is.
Hereinafter, each component contained in the coloring liquid according to this embodiment will be described.

[Water-insoluble colorants A to D]
Examples of the water-insoluble colorants A to D according to the present invention include pigments, disperse dyes, oil-soluble dyes and the like, and disperse dyes and oil-soluble dyes are preferable.

[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 spectroscopic absorption of the DMF solution, and 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. 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. I. Solvent green 5 and the like can be mentioned, preferably C.I. I. Disperse Yellow 54, 82, 232, C.I. I. Disperse Yellow 54 is more preferred. Further, the water-insoluble colorant A may be used alone or in combination of two or more.

[Water-insoluble colorant B]
The water-insoluble colorant B is not particularly limited as long as it is a colorant having a wavelength longer than 450 nm in ultraviolet-visible spectroscopic absorption of a DMF solution and a maximum absorption wavelength in a wavelength range of 470 nm or shorter. Examples of the insoluble colorant B include, for example, C.I. I. Disperse Brown 26, 27, etc. are mentioned, and C.I. I. Disperse brown 27 is preferred. Further, the water-insoluble colorant B may be used alone or in combination of two or more.

[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 range of 590 nm to 640 nm in the ultraviolet-visible spectroscopic absorption of the 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. I. Solvent Blue 35, 36, 78, 111, 112, C.I. I. Examples thereof include Solvent Violet 13, preferably C.I. I. Disperse Blue 72, 360, C.I. I. Solvent Violet 13 and C.I. I. Disperse Blue 360 is more preferred. Further, the water-insoluble colorant C may be used alone or in combination of two or more.

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

The coloring liquid may further contain other water-insoluble coloring agents other than the water-insoluble coloring agents A to D. The other water-insoluble colorant is not particularly limited as long as it is a water-insoluble colorant not contained in any of the above water-insoluble colorants A to D, and is selected from disperse dyes, oil-soluble dyes, pigments and the like. ..

The DMF solution described in each item of the water-insoluble colorants A to D is obtained by dissolving or dispersing the water-insoluble colorants A to D in DMF (N, N-dimethylformamide), respectively, in ultraviolet-visible spectroscopic absorption. Represents a solution whose concentration has been adjusted so that the absorbance at the maximum absorption wavelength is 1.

When 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 formula (D) / ( The value calculated by 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, and more preferably 0.05. It is particularly preferably more than or equal to 0.75 or less, and extremely preferably 0.1 or more and 0.7 or less.

When the absorbance of the maximum absorption wavelength of the water-insoluble colorant A in the DMF solution is 1, the a ^* value of the CIE color space is in the range of -25 to -10, and the water-insoluble colorant B is used. It is one of the preferable forms that the a ^* value of the CIE color space is in the range of 15 to 35 when the absorbance of the maximum absorption wavelength in the DMF solution is 1.

The water-insoluble colorants A to D and other water-insoluble colorants (hereinafter, these may be simply abbreviated as colorants) may be powdery or lumpy dry colorants, wet cakes or slurries. For the purpose of suppressing the aggregation of the colorant particles during and after the colorant synthesis, a dispersant such as a surfactant may be contained in a small amount. There are grades of commercially available dyes for industrial dyeing, resin coloring, ink, toner, inkjet, etc., and the manufacturing method, purity, particle size, etc. are different from each other. In order to suppress the cohesiveness after pulverization, a color material having smaller particles is preferable, and a material having as few impurities as possible is preferable from the viewpoint of affecting dispersion stability and ink ejection accuracy.

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

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 Sulphonic acid copolymers, polyester-acrylic acid copolymers, polyester-acrylic acid-acrylic acid ester copolymers, polyester-methacrylic acid copolymers, polyester-methacrylic acid-acrylic acid copolymer esters; etc. .. 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, the dispersant is a styrene- (meth) acrylic copolymer, a formalin condensate of aromatic sulfonic acid or a salt thereof, polyoxyethylene arylphenyl ether, polyoxyethylene phenyl ether sulfate, polyoxyethylene. Those containing at least one dispersant selected from the group consisting of naphthyl ether are preferable. The content of the dispersant in the coloring 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 styrene-acrylic acid-based copolymer 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 resin in water deteriorates, and especially when the water-insoluble colorant is a dispersible dye, the dispersion stabilizing power tends to be inferior, and if the acid value becomes too large, it becomes an aqueous medium. This is not preferable because the affinity of the dye becomes stronger and the image after printing tends to cause bleeding. The acid value of the resin represents the number of mg of KOH required to neutralize 1 g of the resin, and is measured according to JIS-K3054. Further, the glass dislocation 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 Jonclyl 678 is more preferable.

The coloring liquid can be prepared by using two or more kinds of styrene-acrylic copolymers at the time of dispersing or dissolving the water-insoluble colorants A to D and other water-insoluble colorants.

Dispersion of the water-insoluble colorants A to D and other water-insoluble colorants can be performed by, for example, the following method. A styrene-acrylic copolymer is put into a water-soluble organic solvent, the temperature is raised to 90-120 ° C. to prepare a styrene-acrylic copolymer solution, and an alkaline compound and water are put into the solution to prepare a temperature. Is reduced to an emulsified (emulsion or microemulsion) liquid, and the prepared emulsion liquid and a colorant are mixed and dispersed.

The formalin condensate of aromatic sulfonic acid or a salt thereof is an anionic surfactant obtained by a condensation reaction of 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-naphthalin 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 and lignin 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 the formalin condensate of β-naphthalene sulfonic acid, Demor C is the formalin condensate of creosote oil sulfonic acid; and Demor SN-B is the 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, Emargen A-500 (all manufactured by Kao Corporation); and the like.

Examples of the polyoxyethylene aryl phenyl ether sulfate include the polyoxyethylene styryl phenyl ether sulfate described above. 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 and SM-210 (all manufactured by Toho Chemical Industry Co., Ltd.).

Examples of commercially available products of the 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.

In addition to the above, the coloring liquid according to the present embodiment may further contain a conventionally known nonionic 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.

Examples of the surfactant include known surfactants such as anion-based, cationic-based, nonionic-based, and silicone-based. 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 sul sulfo sulphate, dioctyl sulfo sulphate and the like. 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 surfactant include betaine lauryldimethylaminoacetate, 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) type; manufactured by Nisshin Kagaku Co., Ltd., trade names: Surfinol 104, 105, 82, 465, olphin STG, etc .; ); And so on.

Examples of the silicone-based surfactant include polyether-modified siloxane and polyether-modified polydimethylsiloxane. 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 preferably has 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.

It is preferable that the coloring liquid further contains 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). Ethylene oxide adduct of phytosterol) and the like. Examples of commercially available products of alkylene oxide adducts of cholestanols include NIKKOL DHC-30 (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 additives include water-soluble organic solvents, preservatives, pH adjusters, chelating reagents, rust preventives, water-soluble ultraviolet absorbers, water-soluble polymer compounds, viscosity regulators, dye solubilizers, and anti-fading agents. , Antioxidants and the like.

Examples of the water-soluble organic solvent include glycol-based solvents, polyhydric alcohols, pyrrolidones and the like. 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, 1,3-butanediol, and 1, , 4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3 -Polyhydric alcohols such as methyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, glycerin, trimethylolpropane, 1,3-pentanediol, 1,5-pentanediol, etc. Examples thereof include 2-pyrrolidone and N-methyl-2-pyrrolidone, and it is preferable that at least either glycerin or diglycerin is contained. 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 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 alcohol other than glycerin) is preferable. It is preferable to use in combination with. The total content of the water-soluble organic solvent 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-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. Thiazol-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. Examples thereof include -2-methyl-4-isothiazolin-3-onemagnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-oncalcium chloride, 2-methyl-4-isothiazolin-3-onecalcium chloride and the like. .. Specific examples of other antiseptic and antifungal agents include acetic anhydride, sodium sorbate or sodium benzoate, manufactured by Arch Chemical Co., Ltd., trade names: Proxel ^RTM GXL (S), Proxel ^RTM XL-2 (S) and the like.

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 prepared 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. Triethanolamine 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 agent include acidic sulfite, sodium thiosulfate, ammonium thioglucolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.

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

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

Examples of the viscosity adjusting agent 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 anti-fading agent is used for the purpose of improving the storage stability of an 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 antioxidant, for example, various organic and metal complex-based anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromanes, alkoxyanilines, heterocycles and the like. ..

In the coloring liquid, it is preferable that the additive contains at least one 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.

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, vinyl chloride, vinyl acetate, polyvinyl). There are emulsions formed from 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.

The urethane resin is often sold in the form of a latex (emulsion), and most of them are emulsified liquids 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. Examples thereof include hydroxides and triethylamines. 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 adjuster, 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 A to D and other water-insoluble colorants are dispersed may be mixed. ..

A dyeing bath containing the above-mentioned coloring liquid is also included in the present invention.

The prepared coloring liquid and the ink containing the coloring liquid may be subjected to microfiltration 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.

From the viewpoint of high-speed ejection response, the viscosity of the ink at 25 ° C. is preferably about 3 to 20 mPa · s as measured by an E-type viscometer. 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.

An ink set containing the above ink and other inks 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 examples thereof include yellow ink, magenta ink, cyan ink, orange ink, violet ink, green ink, turquoise ink, and blue ink. , Not as far as shown here. In addition, light yellow ink, light magenta ink, light cyan ink, and light black ink, which are inks (low density ink or high density ink) in which the total concentration of the colorant in the ink is changed with respect to the above ink or the above other inks. And so on.

Examples of the colorant that may be contained in the 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, 184: 1, 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 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, 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 mag; 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 .; and the like.

Specific examples of the oil-soluble dye include, for example, C.I. I. Solvent Yellow 2,6,14,16,21,25,29,30,33,51,56,77,80,82,88,89,93,116,150,163,179,160: 1 etc .: C .. 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 Brown 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 may be used alone or in combination of two or more.

A recording medium obtained by using the above-mentioned coloring liquid or an ink containing the coloring liquid is also included in the present invention.

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 fiber include polyester fiber, nylon fiber, triacetate fiber, diacetate fiber, polyamide fiber, and blended fiber using two or more kinds 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.

The coloring liquid or the ink containing the coloring liquid can be used in various fields, but is suitable for water-based writing inks, water-based printing inks, information recording inks, printing, etc., and can be used as inkjet printing inks. Especially preferable.

A printing step of obtaining a recorded image by adhering to a droplet intermediate recording medium of the coloring liquid or the ink containing the coloring liquid, and hydrophobic fibers on the adhesion surface of the coloring liquid or the ink containing the coloring liquid in the intermediate recording medium. Also included in the present invention is a method for printing a hydrophobic fiber, including a transfer step of transferring the recorded image to the hydrophobic fiber by contacting and heat-treating the image. Further, the present invention also includes an intermediate recording medium to which a coloring liquid or an ink containing the coloring liquid is attached.

The 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 droplets of ink containing the coloring liquid are attached to hydrophobic fibers by an inkjet printer. Step A for forming image information such as characters and patterns on hydrophobic fibers, and the coloring liquid adhered by the step A or the sublimation dye in the ink droplets containing the coloring liquid are fixed to the fibers by heat. It is a method for printing a hydrophobic fiber, which comprises at least three steps of step B and step C for 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, the ink containing the coloring liquid, or the droplets of the ink set are subjected 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 adhering surface of the coloring liquid or the ink droplets containing the coloring liquid in the intermediate recording medium and heat-treated. This is a method for printing hydrophobic fibers, which transfers recorded images such as characters and patterns recorded on an intermediate recording medium to the hydrophobic fibers. As the intermediate recording medium, when the coloring liquid adhering to the intermediate recording medium or the sublimation dye in the ink containing the coloring liquid does not aggregate on the surface thereof and the recorded image is transferred to the hydrophobic fiber, the intermediate recording medium is used. Those that do not interfere with the sublimation of the dye are preferable. An example of such an intermediate recording medium is a paper having a colored liquid 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. for 30 to 1 minute, is also possible.

The 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 glue material, 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 formicate and 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 glutinous agent, 0.5 to 5% for sodium hydrogen carbonate, and metanitrobenzene sulfonic acid on a mass basis. Sodium is 0-5%, urea is 1-20%, and the rest is water. The application of the pretreatment agent to the cellulosic fiber may be, for example, a padding method. The padding ratio is preferably about 40 to 90%, more preferably about 60 to 80%.

The coloring liquid of the present invention or an ink containing the coloring liquid is excellent in storage stability without solid precipitation, physical characteristic change, color change, etc. after long-term storage. In addition, the initial filling property to the inkjet printer head is good, and the continuous printing stability is also good. Further, it is possible to obtain a clear image without blurring of the image on the paper after printing. In addition to these, the dyed product dyed with the above-mentioned coloring liquid of the present invention or an ink containing the coloring liquid has a high dyeing concentration, excellent leveling property, and a high-quality black hue. Furthermore, full-color inkjet printing with excellent fastness and storage stability is possible. As described above, the coloring liquid of the present invention or the ink containing the coloring liquid is particularly suitable for inkjet printing ink because it is extremely excellent in ejection stability. In particular, the value of the dyeing density is as high as 340 or more, which is the color-developing density represented by Sigma K / S in the following dyeing density evaluation, and the black color is extremely excellent in color rendering. Therefore, it is more excellent as the above-mentioned coloring liquid or an ink containing the coloring liquid.

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

[Preparation Example 1: Preparation of Joncryl 678 Emulsion Solution]
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 water-insoluble colorant, Kayaset Yellow AG (manufactured by Nippon Kayaku Co., Ltd., CI Disperse Yellow 54, a ^* value is -20) (10 parts), Laberin W-40 (Cleosoto oil sulfonate sodaformalmarin) Aqueous solution of polycondensate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (15 parts), NIKKOL BPS-30 (0.8 parts), Surfinol 104PG50 (Surfinol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) To a 50% concentration diluted with propylene glycol) (0.2 parts), Proxel GXL (S) (manufactured by Ronza) (0.1 parts), and ion-exchanged water (73.9 parts). 0.2 mm diameter glass beads were added, and the dispersion treatment was performed 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 1.
[Preparation Example 3: Preparation of Aqueous Dispersion Liquid 2]
A water-insoluble colorant is commercially available from C.I. I. An aqueous dispersion 2 was obtained in the same manner as in Preparation Example 2 except that the mixture was changed to Disperse Orange 25.
[Preparation Example 4: Preparation of Aqueous Dispersion Liquid 3]
A water-insoluble colorant is commercially available from C.I. I. An aqueous dispersion 3 was obtained in the same manner as in Preparation Example 2 except that the solvent was changed to Solvent Orange 60.
[Preparation Example 5: Preparation of Aqueous Dispersion Liquid 4]
A water-insoluble colorant is commercially available from C.I. I. An aqueous dispersion 4 was obtained in the same manner as in Preparation Example 2 except that it was changed to Disperse Brown 27 (a ^* value is 30).
[Preparation Example 6: Preparation of Aqueous Dispersion Liquid 5]
A water-insoluble colorant is commercially available from C.I. I. An aqueous dispersion 5 was obtained in the same manner as in Preparation Example 2 except that the mixture was changed to Disperse Blue 359.
[Preparation Example 7: Preparation of Aqueous Dispersion Liquid 6]
A water-insoluble colorant is commercially available from C.I. I. An aqueous dispersion 6 was obtained in the same manner as in Preparation Example 2 except that the mixture was changed to Disperse Blue 360.
[Preparation Example 8: Preparation of Aqueous Dispersion Liquid 7]
As a water-insoluble colorant, Kayaset Yellow AG (manufactured by Nippon Kayaku Co., Ltd., CI Disperse Yellow 54) (10 parts), Joncryl 678 emulsion (30 parts), Surfinol 104PG50 (Surfinol 104 (Surfinol 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 Ronza Co., Ltd.) (0.1 parts), and 0.2 mm diameter glass beads were added to the mixture consisting of ion-exchanged water (59.7 parts), and the mixture was dispersed under cooling with a sand mill 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 7.
[Preparation Example 9: Preparation of Aqueous Dispersion Liquid 8]
A water-insoluble colorant is commercially available from C.I. I. An aqueous dispersion 8 was obtained in the same manner as in Preparation Example 8 except that the mixture was changed to Disperse Brown 27.
[Preparation Example 10: Preparation of Aqueous Dispersion Solution 9]
A water-insoluble colorant is commercially available from C.I. I. An aqueous dispersion 9 was obtained in the same manner as in Preparation Example 8 except that the mixture was changed to Disperse Blue 359.
[Preparation Example 11: Preparation of Aqueous Dispersion Liquid 10]
A water-insoluble colorant is commercially available from C.I. I. An aqueous dispersion 10 was obtained in the same manner as in Preparation Example 8 except that the mixture was changed to Disperse Blue 360.
[Preparation Example 12: Preparation of Aqueous Dispersion Liquid 11]
As a water-insoluble colorant, Kayaset Yellow AG (manufactured by Nippon Kayaku Co., Ltd., CI Disperse Yellow 54) (10 parts), SM-57 (manufactured by Toho Chemical Industry Co., Ltd., polyoxyethylene styrylphenyl ether sulfate) Dispersant) (10 parts), Surfinol 104PG50 (Surfinol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted to 50% concentration with propylene glycol) (0.2 parts), Proxel GXL (S) Add 0.2 mm diameter glass beads to the mixture consisting of (0.1 part) (made by Ronza) and ion-exchanged water (79.7 parts), cool with a sand mill, and disperse for about 15 hours. went. 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 11.
[Preparation Example 13: Preparation of Aqueous Dispersion Liquid 12]
A water-insoluble colorant is commercially available from C.I. I. An aqueous dispersion 12 was obtained in the same manner as in Preparation Example 12 except that the mixture was changed to Disperse Brown 27.
[Preparation Example 14: Preparation of Aqueous Dispersion Liquid 13]
A water-insoluble colorant is commercially available from C.I. I. An aqueous dispersion 13 was obtained in the same manner as in Preparation Example 12 except that the mixture was changed to Disperse Blue 359.
[Preparation Example 15: Preparation of Aqueous Dispersion Liquid 14]
A water-insoluble colorant is commercially available from C.I. I. An aqueous dispersion 14 was obtained in the same manner as in Preparation Example 12 except that the mixture was changed to Disperse Blue 360.
[Preparation Example 16: Preparation of Example Ink and Comparative Example Ink]
The aqueous dispersions 1 to 14 obtained above are mixed with each component shown in Table 2 below, stirred for 30 minutes, and then with a glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size: 0.5 μm). By filtering, each ink of Examples 1 to 12 and Comparative Example 1 was prepared. In the table, the numerical value of each component indicates the number of copies added.

The abbreviations and the like in Table 2 indicate the following.
Surfinol 465: Nonionic surfactant TEA80: 80% aqueous solution of triethanolamine manufactured by Nisshin Kagaku Kogyo Co., Ltd.

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

The following evaluation tests were performed using each ink prepared as described above. The results are shown in Table 3 below.

[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 / m2) as an intermediate recording medium, 100% Duty and 40% Duty single colors. Intermediate recording media on which solid images 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. × 30. 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 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. Evaluation was made according to the following evaluation criteria.
[Evaluation criteria]
S: Sigma K / S value is 350 or more.
A: The sigma K / S value is 345 or more and less than 350.
B: The 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 is less than 335.
[Evaluation of color rendering]
The hues L ^* , a ^* , and b ^* of each dyed product were measured using a spectrocolorimeter "Ci62 (manufactured by X-Rite)" for the dyed portion of 40% Duty of each dyed product. For color measurement, the values of L ^* , a ^* , and b ^* of the D65 light source and the A light source were obtained by using the conditions of the viewing angle of 2 ° and the status T. From the values of L ^* , a ^* , and b ^* of each of the obtained light sources, the color difference ΔE _D65-A between the D65 light source and the A light source was obtained from the following equation (Equation 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 formula represent the following.
L ^* _D65 : L ^* value in D65 light source L ^* _A : L ^* value in A light source a ^* _D65 : a ^* value in D65 light source a ^* _A : a ^* value in A light source b ^* _D65 : b ^* value in D65 light source b ^* _A : b ^* value in A light source

When the value of _ΔED65-A calculated by the above formula 3 is smaller, it means that the hue change due to the influence of the color rendering property is suppressed and the quality is high. Evaluation was made according to the following evaluation criteria.
[Evaluation criteria]
S: The value of the color difference ΔE _D65-A is less than 1.8.
A: The value of the color difference _ΔED65-A is 1.8 or more and less than 2.0.
B: The value of the color difference _ΔED65-A is 2.0 or more and less than 2.2.
C: The value of the color difference _ΔED65-A is 2.2 or more and less than 2.4.
D: The value of the color difference ΔE _D65-A is 2.4 or more.

As is clear from the results in Table 3, each of the prepared inks of Examples 1 to 12 has extremely excellent performance of suppressing hue change due to the influence of color rendering property and has excellent color development property as compared with the ink of Comparative Example 1. It showed high results.

The coloring liquid of the present invention can suppress a change in hue due to the influence of color rendering and can obtain a dyed product having excellent color-developing property, and maintain the printability required for various printing inks, especially inkjet printing inks. It is extremely useful because it can be used.

Claims (11)

Water-insoluble colorant A having a maximum absorption wavelength in the wavelength range of 410 nm to 450 nm in the ultraviolet visible spectral absorption of the DMF solution, a wavelength longer than 450 nm and a wavelength of 470 nm or shorter in the ultraviolet visible spectral absorption of the DMF solution. Water-insoluble colorant B having a maximum absorption wavelength in the region, water-insoluble colorant C having a maximum absorption wavelength in the wavelength range of 590 nm to 640 nm in the ultraviolet-visible spectral absorption of the DMF solution, longer than 640 nm in the ultraviolet-visible spectral absorption of the DMF solution. In a coloring liquid containing a water-insoluble coloring agent D having a maximum absorption wavelength in a wavelength range of 700 nm or shorter, the content of the water-insoluble coloring agent D in the coloring liquid is (D). , When 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. The coloring liquid according to claim 1, further comprising a dispersant, a surfactant and water. When the absorbance of the maximum absorption wavelength of the water-insoluble colorant A in the DMF solution is 1, the a ^* value of the CIE color space is in the range of -25 to -10, and the water-insoluble colorant B is used. The coloring solution according to claim 1 or 2, wherein the a ^* value of the CIE color space is in the range of 15 to 35 when the absorbance of the maximum absorption wavelength in the DMF solution is 1. The coloring liquid according to any one of claims 1 to 3, wherein the value calculated by the above formula (D) / (A + C) is 0.03 or more and less than 0.8. 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 any one of claims 2 to 4, which comprises at least one selected from the group. The coloring liquid according to claim 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. 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. The coloring liquid according to any one of claims 1 to 7, further comprising a phytosterol-based compound. A recording medium obtained by using the coloring liquid according to any one of claims 1 to 8. The recording medium according to claim 9, wherein the recording medium is a hydrophobic fiber. A printing step in which droplets of the coloring liquid according to any one of claims 1 to 8 are attached to an intermediate recording medium to obtain a recorded image, and hydrophobic fibers are attached to the adhesion surface of the coloring liquid in the intermediate recording medium. A method for printing a hydrophobic fiber, which comprises a transfer step of transferring the recorded image to the hydrophobic fiber by contacting and heat-treating the image.