JP7332265B2 - Colored dispersion and method for printing hydrophobic fibers - Google Patents

Description

Colored dispersion containing (A) a compound represented by the following formula (1), (B) a polyoxyethylene arylphenyl ether-based dispersant and a polyoxyethylene arylphenyl ether sulfate-based dispersant, and a record to which these adhere It relates to a method for printing media and hydrophobic fibers.

2. Description of the Related Art In recent years, there has been proposed a recording method in which ink jet printing is performed without plate making, and ink jet printing is also used for textile printing of fibers including cloth. Compared to conventional textile printing methods such as screen printing, textile printing by inkjet printing has various advantages such as no plate making, resource saving, energy saving, and easy high-definition expression. There are advantages. Hydrophobic fiber cloth such as polyester fiber is generally dyed with a water-insoluble colorant. Therefore, as a water-based ink for printing hydrophobic fibers by an inkjet recording method, it is generally necessary to use a dispersion ink that disperses a water-insoluble colorant in water and has good performance such as dispersion stability. The ink jet printing method for hydrophobic fibers represented by polyester fibers can be broadly classified into the following two methods. After applying ink directly to the fiber (printing), the dye in the ink is dyed to the fiber by heat treatment such as high temperature steaming. ), the ink-applied surface of the intermediate recording medium and the hydrophobic fiber are superimposed, and then the dye is transferred from the intermediate recording medium to the fiber side by heat.

Among the above methods, the sublimation transfer method is mainly used for printing banners and the like, and an easily sublimable dye that is excellent in transferability 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 process: a process of transferring and dyeing the dye from the intermediate recording medium to the fiber by heat treatment;
Since commercially available transfer paper can be widely used, no pretreatment of the fibers is required, and the washing step is also omitted.

The inkjet ink used in the sublimation transfer method is mainly a water-based ink, and a sublimation dye selected from the water-insoluble disperse dye group and the oil-soluble dye group is dispersed in water using a dispersant to stabilize the dispersion of fine particles. 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/antifungal agent, antifoaming agent, etc.) is used to optimize physical properties (physical properties) such as particle size, viscosity, surface tension, and pH (see Patent Document 1). In inkjet printing, it is important to be able to stably eject ink from the plate on which the nozzles of the print head are arranged. Easy to happen. As the ejection trouble, for example, when the ink composition adheres and dries on the plate, it cannot be quickly removed by the cleaning operation of the printer, causing ink ejection failure (flight deflection, etc.) during printing. etc. In order to solve these problems, for example, 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 as a black hue and often has a low density. By combining a plurality of dyes, it is possible to express a good black color. However, when the fabric is dyed with a black ink that is a combination of a plurality of dyes having sublimation properties, when the fabric is irradiated with light with a different spectral distribution of the light source depending on the type of fabric, the black color expressed on the fabric In some cases, the colors appeared to have different hues. For example, even if good colors can be expressed under lighting such as fluorescent lighting, which has little long-wavelength light, it may appear reddish under sunlight, which has many long-wavelength lights, or vice versa. Even if the color could be expressed well under a fluorescent light, it sometimes looked bluish. Thus, the characteristic that affects how the color of an object is viewed by an illumination light source is generally called "color rendering", and there has been a demand for a black ink that causes little change in hue due to the effect of this color rendering. Furthermore, inkjet inks are also required to have good ejection properties. In the case of a black ink in which a plurality of dyes are combined to increase the types and amounts of sublimation dyes, there are problems in the ejection stability and storage stability of the ink.

On the other hand, in the printing method of hydrophobic fibers in the sublimation transfer method, sublimation transfer ink is applied (printed) to an intermediate recording medium (dedicated transfer paper, etc.) with an inkjet printer, and the ink applied (printed) surface of the intermediate recording medium Sublimation dyes are transferred to the object to be dyed (polyester fiber, etc.) by a thermocompression bonding method using a thermocompression roller, a heat press, or the like. In commercial printing, inkjet printing is becoming faster, and there is a demand for inkjet inks designed to cope with the increased speed. In addition, as an intermediate recording medium for sublimation transfer ink, an ink-receiving layer is formed on the surface with inorganic fine particles such as silica. However, in recent years, transfer paper with a smaller basis weight or a less 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 a black ink that does not change its black hue depending on sublimation transfer conditions and that has a uniform sublimation speed. Patent Document 2 discloses an inkjet black ink used as a disperse dye ink for textile printing. Ink jet black inks characterized by containing first to fourth disperse dyes having absorption wavelengths are described, although inks applied directly to pretreated polyester fibers in the direct printing method are mentioned. However, there is no technical study on sublimable dyes that can be used in the sublimation transfer method, and no disclosure is made on levelness and dyeing performance in high-density dyeing.

WO2005/121263 Japanese Patent No. 6191234

INDUSTRIAL APPLICABILITY In sublimation transfer dyeing using inkjet textile printing, the present invention can produce a dyed product with excellent color rendering properties, high sublimation transfer efficiency, and a high-quality dyed product that can obtain a high-density dyed product. It is an object of the present invention to provide a colored dispersion for an inkjet textile ink which can be formed and has excellent redispersibility.

The present inventors have made intensive studies to solve the above-described problems, and found that (A) a compound represented by the following formula (1), (B) a polyoxyethylene arylphenyl ether-based dispersant and a polyoxy The inventors have found that a colored dispersion containing an ethylene arylphenyl ether sulfate-based dispersant solves the above problems, and have completed the present invention.

That is, the present invention relates to the following 1) to 9).
1)
A colored dispersion containing (A) a compound represented by the following formula (1), and (B) a polyoxyethylene arylphenyl ether-based dispersant and a polyoxyethylene arylphenyl ether sulfate-based dispersant.

(In formula (1), R ¹ represents a hydrogen atom or a nitro group. R ² and R ³ each independently represents a C1-C4 alkyl group optionally substituted with a C1-C4 alkoxy group or a phenyl group. ^.R4 represents a halogen atom.In addition, ^R2 and ^R3 may be linked to each other to form a ring.)
2)
The colored dispersion according to 1), wherein R ⁴ in the above formula (1) is a chlorine atom or a bromine atom.
3)
1) wherein R ¹ in the above formula (1) is a hydrogen atom, R ² and R ³ are each independently a C1-C4 alkyl group optionally substituted with a C1-C4 alkoxy group, and R ⁴ is a chlorine atom; Colored dispersion as described.
4)
The colored dispersion according to any one of 1) to 3) further comprising a water-soluble organic solvent.
5)
One type of yellow dye, one type of blue dye having a maximum absorption wavelength in the wavelength range of 620 nm or more and less than 700 nm in the ultraviolet-visible spectral absorption of the solution dissolved in acetone, and the ultraviolet-visible spectral absorption of the solution dissolved in acetone , and one type of blue dye having a maximum absorption wavelength in a wavelength range of 550 nm or more and less than 620 nm.
6)
A recording medium to which the colored dispersion according to any one of 1) to 5) is adhered.
7)
The recording medium according to 6), wherein the recording medium is a fiber.
8)
The recording medium according to 7), wherein the fibers are hydrophobic fibers.
9)
The recording medium according to 8), wherein the hydrophobic fiber is polyester or a blended fiber containing polyester.

According to the present invention, in sublimation transfer dyeing using inkjet textile printing, it is possible to produce a dyed product with little change in hue due to the effect of color rendering, high sublimation transfer efficiency, and a high-quality black color that can obtain a high-density dyed product. can be obtained, and a colored dispersion for inkjet textile inks having excellent redispersibility can be obtained.

The present invention will be described in detail below. In this specification, including examples, all "parts" and "%" are based on mass unless otherwise specified. Moreover, in this specification, "C.I." means "color index."

The colored dispersion contains at least one compound represented by the formula (1).

In formula (1), ^R1 represents a hydrogen atom or a nitro group. R ² and R ³ each independently represent a C1-C4 alkyl group optionally substituted with a C1-C4 alkoxy group or a phenyl group. ^R4 represents a halogen atom. Also, R ² and R ³ may be linked together to form a ring.
The C1-C4 alkyl group which may be substituted with a C1-C4 alkoxy group or a phenyl group includes a C1-C4 alkyl group, a C1-C4 alkyl group substituted with a C1-C4 alkoxy group, and a C1-C4 alkyl group substituted with a phenyl group. and C1-C4 alkyl groups.

Examples of the C1-C4 alkyl groups include linear alkyl groups such as methyl group, ethyl group, n-propyl group and n-butyl group; Cyclic alkyl groups such as chain alkyl groups and cyclobutyl groups are included.

Examples of the C1-C4 alkyl group substituted with the C1-C4 alkoxy group include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, butoxybutyl group, and the like.

Examples of the C1-C4 alkyl group substituted with a phenyl group include a benzyl group, a phenylethyl group, a phenylpropyl group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, preferably a chlorine atom or a bromine atom, more preferably a chlorine atom.

R ² and R ³ in the above formula (1) may be linked together to form a ring. Examples of the ring formed by connecting R ² and R ³ include a piperidine ring, a piperazine ring, a morpholine ring and the like, and it is preferable to form a piperidine ring.

In the above formula (1), R ¹ is preferably a hydrogen atom, R ² and R ³ are each independently a C1-C4 alkyl group optionally substituted with a C1-C4 alkoxy group, R ⁴ is preferably a chlorine atom, and R More preferably, ¹ is a hydrogen atom, R ² and R ³ are each independently an ethyl group which may be substituted with a methoxy group, R ⁴ is a chlorine atom, R ¹ is a hydrogen atom, and both R ² and R ³ are A methoxyethyl group, ^R4 is a combination of chlorine atoms, ^R1 is a hydrogen atom, ^R2 and ^R3 are each an ethyl group, ^R4 is a combination of chlorine atoms, ^R1 is a hydrogen atom, and any of ^R2 and ^R3 A combination of a methoxyethyl group on one side and an ethyl group on the other and a chlorine atom for ^R4 is highly preferred.

In addition to the above, R ¹ is a hydrogen atom, R ² and R ³ are connected to each other to form a morpholine ring, R ⁴ is a combination of chlorine atoms, R ¹ is a hydrogen atom, R ² and R ³ are connected to each other form a piperidine ring, R ⁴ is a combination of chlorine atoms, R ¹ is a hydrogen atom, one of R ² and R ³ is an iso-propyl group and the other is an ethyl group, R ⁴ is a combination of chlorine atoms, R ¹ is a hydrogen atom, R ² and R ³ are both ethyl groups, R ⁴ is a combination of bromine atoms, R ¹ is a hydrogen atom, one of R ² and R ³ is a benzyl group and the other is an ethyl group, R It is also preferred that ⁴ is a combination of chlorine atoms.

The compound represented by the above formula (1) can be obtained, for example, by diazotizing the compound represented by the following formula (2) by a conventional method, and combining the obtained diazo compound with the compound represented by the following formula (3). It can be obtained by coupling reaction according to the method. R ¹ to R ⁴ in formulas (2) and (3) below are the same as in formula (1) above.

The compound represented by the above formula (1) obtained as described above can be purified, if necessary, by known methods such as acid precipitation, salting out, suspension purification, and crystallization. .

In the colored dispersion containing the compound represented by the formula (1), the compound represented by the formula (1) can be used singly or in combination of two or more. When the above are used in combination, their mass ratio can be set arbitrarily.

Disperse dyes are classified into blue dyes, cyan dyes, red dyes, yellow dyes, orange dyes, and the like according to their maximum absorption wavelengths. In order to obtain a black color tone, it is preferable to use a mixture of these dyes. By combining disperse dyes with different maximum absorption wavelengths, the distribution of spectral absorption intensity is reduced in all regions from the short wavelength side to the long wavelength side, creating an ink with a black hue that has little effect on color rendering. be able to. By containing a yellow dye and a blue dye in addition to the compound represented by the formula (1), the colored dispersion can have a good black hue. In particular, in addition to the compound represented by the above formula (1), one kind of yellow dye and a blue dye having a maximum absorption wavelength in the wavelength range of 620 nm or more and less than 700 nm in the ultraviolet-visible spectral absorption of a solution dissolved in acetone It is preferable to contain one kind of dye and one kind of blue dye having a maximum absorption wavelength in the wavelength region of 550 nm or more and less than 620 nm in the ultraviolet-visible spectral absorption of a solution dissolved in acetone.

[About yellow dye]
The yellow dye is not particularly limited as long as it generally has a yellow hue, but it is preferably a water-insoluble yellow dye, and among the water-insoluble yellow dyes, disperse dye yellow C.I. dyes or oil-soluble yellow dyes are more preferred. I. Disperse Yellow dye, C.I. I. Solvent Yellow dyes are more preferred. C. I. Disperse Yellow dyes include, for example, C.I. I. Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 64, 71, 79, 82, 86 and the like. C. I. Solvent Yellow dyes include, for example, C.I. I. Solvent Yellow 114, 163 and the like. These dyes can be used singly or in combination. Examples of the yellow dye include C.I. I. Disperse Yellow 7, 54, C.I. I. Solvent Yellow 114 is preferably used, preferably C.I. I. It is particularly preferred to use Disperse Yellow 54.

[About blue dye]
The blue dye is not particularly limited as long as it generally has a blue hue, but it is preferably a water-insoluble blue dye, and among the water-insoluble blue dyes, disperse dye blue It is more preferably a blue dye based on C.I. dyes or oil-soluble dyes. I. Disperse Blue dye, C.I. I. Solvent Blue dyes are more preferred. C. I. Disperse Blue dyes include, for example, C.I. I. Disperse Blue 3, 5, 19, 26, 26:1, 35, 55, 56, 58, 60, 64, 64:1, 72, 72:1, 81, 81:1, 91, 95, 108, 131, 141, 145, 334, 359, 360, 336 and the like. C. I. Solvent Blue dyes include, for example, C.I. I. Solvent Blue 3, 36, 63, 83, 105, 111 and the like. These dyes can be used singly or in combination. As the blue dye, C.I. I. Disperse Blue 60, 72, 334, 359 and 360 are preferred, and C.I. I. Disperse Blue 359, 360 are more preferred, and C.I. I. More preferably, Disperse Blue 359 and 360 are used in combination. The C.I. I. Disperse Blue 360 is a blue dye having a maximum absorption wavelength in the wavelength region of 550 nm or more and less than 620 nm in the ultraviolet-visible spectral absorption of the solution dissolved in the acetone. I. Disperse Blue 359 is a blue dye that has a maximum absorption wavelength in the wavelength region of 620 nm or more and less than 700 nm in the ultraviolet-visible spectral absorption of the solution dissolved in acetone.

The total content of the compound represented by formula (1), the yellow dye, and the blue dye in the colored dispersion can be set arbitrarily. On the other hand, it is usually 1 to 20%, preferably 2 to 15%, more preferably 3 to 10% on a mass basis (% by mass).

[Other dyes that may be contained in the colored dispersion]
The colored dispersion liquid may contain other dyes in addition to the compound represented by formula (1), the yellow dye, and the blue dye. As the other dyes, for example, the dyeing fastness test method for dry heat treatment [JIS L 0879: 2005] (confirmed in 2010, revised on January 20, 2005, published by the Japanese Standards Association), "ISO 105-P01 , Textiles-Tests for color fastness-Part P01: Color fastness to dry heat (excluded pressing) ”, the test result of heat-sensitive test (C method) staining (polyester) is preferably grade 3-4 or less, more preferably 3 Class and lower dyes. Among such known dyes, C.I. I. Examples of dyes having numbers include the following dyes.

Other yellow dyes in the other dyes include, for example, C.I. I. Disperse Yellow dyes and C.I. I. Examples of solvent yellow dyes include those other than those exemplified as the above yellow dyes. These dyes can be used singly or in combination.

Other blue dyes in the other dyes include, for example, C.I. I. Disperse Blue dye and C.I. I. Examples of solvent blue dyes include those other than those exemplified as the above blue dyes. These dyes can be used singly or in combination.

Other orange dyes in the other dyes include, for example, C.I. I. Disperse Orange 1, 1:1, 5, 7, 11, 13, 20, 23, 25, 25:1, 29, 33, 56, 73, 76, 113, 114, 123, 147; I. Solvent Orange 60, 67 and the like. These dyes can be used singly or in combination.

Other brown dyes in the other dyes include, for example, C.I. I. Disperse Brown 1, 3, 22, 26, 27; These dyes can be used singly or in combination.

Other red dyes in the other dyes include, for example, C.I. I. Disperse Red 4, 11, 50, 53, 55, 55:1, 59, 60, 65, 70, 75, 92, 93, 146, 158, 190, 190: 1, 207, 239, 240, 364; I. Solvent Red 146; I. Vat Red 41; These dyes can be used singly or in combination.

Other violet dyes in the above other dyes include, for example, C.I. I. Disperse Violet 8, 11, 17, 23, 26, 27, 28, 29, 36, 57, 63; These dyes can be used singly or in combination.

Each of the above dyes may be a powdery or lumpy dry colorant, a wet cake or a slurry, and contains a small amount of a dispersant such as a surfactant for the purpose of suppressing aggregation of the colorant particles during or after the synthesis of the colorant. It may be something else. Commercially available dyes include grades for industrial dyeing, resin coloring, ink, toner, inkjet, and the like, and the manufacturing methods, purities, particle sizes, and the like differ from each other. In order to suppress agglomeration after pulverization, the coloring material preferably has smaller particles, and it preferably contains as few impurities as possible in view of the influence on dispersion stability and ink ejection accuracy. As for dyes, it is possible to use as a coloring material for black by blending yellow dyes, orange dyes and red dyes mainly with blue dyes. Also, a small amount of other water-insoluble coloring materials may be contained within the range of color tone adjustment.

The colored dispersion contains a polyoxyethylene arylphenyl ether-based dispersant and a polyoxyethylene arylphenyl ether sulfate-based dispersant.

Specific examples of the polyoxyethylene arylphenyl ether-based dispersant and polyoxyethylene arylphenyl ether sulfate-based dispersant include polyoxyethylene monostyrylphenyl ether, polyoxyethylene distyrylphenyl ether, polyoxyethylene tri styrylphenol compounds such as styrylphenyl ether and polyoxyethylene tetrastyrylphenyl ether; benzylphenol compounds such as polyoxyethylene monobenzylphenyl ether, polyoxyethylene dibenzylphenyl ether, and polyoxyethylene tribenzylphenyl ether; Examples include cumylphenol compounds such as milphenyl ether, polyoxyethylene naphthylphenyl ether, polyoxyethylene biphenyl ether, polyoxyethylene phenoxyphenyl ether and the like. These can be used singly or in combination. Preferred are polyoxyethylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, polyoxyethylene dibenzylphenyl ether, polyoxyethylene tribenzylphenyl ether and polyoxyethylene cumylphenyl ether. Here, the repeating unit number b of the polyoxyethylene group is an integer of 1-30, preferably an integer of 15-30. When b is an integer of 1 or more, the compatibility with aqueous solvents and other additives is excellent. These are also called arylphenol compounds.

Examples of such arylphenol compounds are those described below. As the styrylphenol compound, for example, commercially available products such as Noigen EA series manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., TS-2000, TS-2600, SM-174N manufactured by Toho Chemical Industry Co., Ltd. can be used. As the benzylphenol compound, for example, a commercial product such as Emulgen B-66 manufactured by Kao Corporation can be used. can be used.
Polyoxyethylene arylphenyl ether dispersants 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 (both manufactured by Takemoto Oil Co., Ltd.), TS-1500, TS-2000, TS-2600, SM-174N (both manufactured by Toho Chemical Co., Ltd.), Emulgen A60, Emulgen A90, Emulgen A500 (Kao ) and the like, and these can be used singly or in combination. Examples of polyoxyethylene arylphenyl ether sulfate-based dispersants include SM-57, SM-130, and SM-210 (all manufactured by Toho Chemical Co., Ltd.), and these can be used alone or in combination. is.

The colored dispersion preferably further contains a dispersant other than the polyoxyethylene arylphenyl ether-based dispersant and the polyoxyethylene arylphenyl ether sulfate-based dispersant, and water.

As the other dispersing agents, for example, styrene-(meth)acrylic copolymers, formalin condensates of aromatic sulfonic acids, or salts thereof can be used. The styrene-(meth)acrylic copolymer is a copolymer of a styrene-based monomer and a (meth)acrylic-based monomer. In this specification, "(meth)acryl" means "acryl" and/or "methacryl". Specific examples of these copolymers include (α-methyl)styrene-acrylic acid copolymers, (α-methyl)styrene-acrylic acid-acrylic ester copolymers, (α-methyl)styrene-methacrylic acid copolymers, Polymer, (α-methyl) styrene-methacrylic acid-acrylate copolymer, (α-methyl) styrene-(anhydride) maleic acid copolymer, acrylic ester-(anhydride) maleic acid copolymer, ( α-methyl)styrene-acrylate-(anhydride) maleic acid copolymer, acrylic ester-allylsulfonic acid ester copolymer, acrylic ester-styrenesulfonic acid copolymer, (α-methyl)styrene-methacryl sulfonic acid copolymer, polyester-acrylic acid copolymer, polyester-acrylic acid-acrylic acid ester copolymer, polyester-methacrylic acid copolymer, polyester-methacrylic acid-acrylic acid copolymer ester; . Among these, styrene is preferred as the compound containing an aromatic hydrocarbon group. (α-Methyl)styrene is used herein to include α-methylstyrene and styrene. In the colored dispersion, the other dispersant is at least one dispersant selected from the group consisting of styrene-(meth)acrylic copolymers, formalin condensates of aromatic sulfonic acids, and salts thereof. preferably containing. The content of other dispersants in the above colored dispersion is generally 1 to 36%, preferably 1 to 30%, more preferably 1 to 20%, still more preferably 1 to 15%.

Specific examples of the above other dispersants include 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, 690 (manufactured by BASF), etc., but not limited thereto. In this specification, the superscript RTM means a registered trademark.

The weight average molecular weight of the other dispersant is preferably 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). Further, the styrene-(meth)acrylic copolymer used as a dispersant preferably has an acid value of 50 to 250 mgKOH/g, more preferably 100 to 250 mgKOH/g, particularly 150 to 250 mgKOH/g. preferable. If the acid value is too small, the solubility of the resin in water deteriorates, and especially when the colorant is a disperse dye, the ability to stabilize dispersion tends to be poor. This is not preferable because the printed image tends to bleed easily. The acid value of a resin represents the number of mg of KOH required to neutralize 1 g of 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 which are other preferred dispersants in the above-mentioned colored dispersion 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 Joncryl 678 is more preferable.

The colored dispersion includes the compound represented by the formula (1), the optionally included yellow dye, the optionally included blue dye, and the other dyes when dispersing or dissolving, in addition to the dispersant, 2 It can be made using more than one type of styrene-acrylic copolymer.

The compound represented by formula (1), the optionally contained yellow dye, the optionally contained blue dye, and other dyes can be dispersed, for example, by the following method. 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, an alkaline compound and water are put therein, and the temperature is is lowered to form an emulsified (emulsion or microemulsion) liquid, and the prepared emulsion liquid and the compound represented by the above formula (1), the optionally included yellow dye, the optionally included blue dye, and other dyes Mix and disperse.

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. "Salts thereof" include salts such as sodium salts, potassium salts and lithium salts. The formalin condensate of aromatic sulfonic acid or a salt thereof is a formalin condensate of aromatic sulfonic acid, a salt thereof, or a mixture thereof (hereinafter referred to as "formalin condensate of sulfonic acid" unless otherwise specified) , which also includes "a salt thereof, or a mixture thereof"), etc. are preferred. For example, 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- Examples include formalin condensates such as naphthol-6-sulfonic acid and ligninsulfonic acid. Among these, formalin condensates of creosote oil sulfonic acid, β-naphthalene sulfonic acid, lignin sulfonic acid and methylnaphthalene sulfonic acid are preferred. These are commercially available under various trade names. Examples include Demol N as a formalin condensate of β-naphthalenesulfonic acid, Demol C as a formalin condensate of creosote oil sulfonic acid, and Demol SN-B as a formalin condensate of a special aromatic sulfonic acid. manufactured by Kao Corporation); Examples of formalin condensates of creosote oil sulfonic acid include Labelin W series, and examples of formalin condensates of methylnaphthalene sulfonic acid include Labelin AN series (both manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). Among these, Demoll N, Labellin AN series, and Labellin W series are preferred, Demoll N and Labellin W are more preferred, and Labellin W is even more preferred. Examples of ligninsulfonic acid include Vanilex N, Vanilex RN, Vanilex G, and Pearllex DP (all manufactured by Nippon Paper Industries Co., Ltd.). Among these, Vanilex RN, Vanilex N, and Vanilex G are preferred.

The colored dispersion may further contain a water-soluble organic solvent.

Examples of the water-soluble organic solvent include glycol-based solvents, polyhydric alcohols, pyrrolidones, and the like. Examples of glycol solvents include glycerin, polyglycerin (#310, #750, #800), diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, un 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. to C3 alkylene glycol, preferably liquid polyalkylene glycol; Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, thiodiglycol, 1,3-butanediol, 1 ,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3 -polyhydric alcohols such as methyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, glycerin, trimethylolpropane, 1,3-pentanediol and 1,5-pentanediol; 2-pyrrolidone, N-methyl-2-pyrrolidone, etc., and preferably contains at least either glycerin or diglycerin. For the sake of 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 thereof include urea, ethylene urea, and sugars. Considering storage stability, when the colorant is a disperse dye or an oil-soluble dye, solvents with low solubility thereof are preferable, and among these, glycerin and solvents other than glycerin (preferably polyhydric alcohols other than glycerin) are preferred. It is preferable to use together with. The total content of the water-soluble organic solvent is 5 to 50%, preferably 10 to 40%, in the total weight of the colored dispersion.

The colored dispersion may further contain additives.

Examples of the above additives include preservatives, surfactants, pH adjusters, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, viscosity modifiers, pigment solubilizers, anti-fading agents, Antioxidants, water and the like can be mentioned.

Examples of the above preservative include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzo Thiazole type, isothiazoline type, dithiol type, pyridine oxide type, nitropropane type, organic tin type, phenol type, quaternary ammonium salt type, triazine type, thiazine type, anilide type, adamantane type, dithiocarbamate type, brominated indanone type , benzyl bromoacetate-based compounds, inorganic salt-based compounds, and the like. Specific examples of organic halogen compounds include sodium pentachlorophenol, specific examples of pyridine oxide compounds include 2-pyridinethiol-1-oxide sodium, and specific examples of isothiazoline compounds. is, for example, 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 and the like. Specific examples of other antiseptic and antifungal agents include sodium acetate anhydride, sodium sorbate, sodium benzoate, trade names Proxel ^RTM GXL (S) and Proxel ^RTM XL-2 (S) manufactured by Arch Chemicals.

Examples of the surfactant include known surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, 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 taurates, alkyl sulfates. Polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate, lauryl alcohol sulfate, alkylphenol type phosphate, alkyl type phosphate, alkylaryl sulfonate, diethylsulfosuccinate, diethylhexylsulfosuccinate, dioctylsulfosuccinate and the like. Specific examples of the commercially available products include Hitenol LA-10, LA-12, LA-16, Neohitenol ECL-30S and ECL-45, all of which are all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. Cationic surfactants include 2-vinylpyridine derivatives, poly-4-vinylpyridine derivatives and the like. Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, imidazoline derivatives, and the like. is mentioned. 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; Esters such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol Acetylene glycol (alcohol) system such as Nissin Kagaku Co., Ltd., trade name Surfynol 104, 105, 82, 465, Olphine STG, etc.; Polyglycol ether system (eg Tergitol 15-S-7 manufactured by SIGMA-ALDRICH) ); and the like.

Examples of the silicone surfactant include polyether-modified siloxane and polyether-modified polydimethylsiloxane. Specific examples of commercially available products include BYK-347 (polyether-modified siloxane); BYK-345 and BYK-348 (polyether-modified polydimethylsiloxane), all of which are manufactured by BYK-Chemie. Examples of fluorine-based surfactants include perfluoroalkylsulfonic acid compounds, perfluoroalkylcarboxylic acid compounds, perfluoroalkylphosphoric acid ester compounds, perfluoroalkylethylene oxide adducts, and perfluoroalkyl ether groups having side chains. and polyoxyalkylene ether polymer compounds having Specific examples of commercially available products include Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30, FS-31 (manufactured by DuPont); PF-151N. , PF-154N (manufactured by Omnova), and the like.

As the pH adjuster, any substance can be used as long as it can control the pH of the solution in the range of about 5 to 11 without adversely affecting the prepared colored dispersion. 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 hydrogen carbonate and potassium carbonate; alkali metal salts of organic acids such as potassium acetate; inorganic bases such as sodium silicate and disodium phosphate; Triethanolamine is preferred.

Specific examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracil diacetate.

Examples of the rust preventive include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate and dicyclohexylammonium nitrite.

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

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

Examples of the viscosity modifier include water-soluble organic solvents as well as water-soluble polymer compounds such as polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.

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

The anti-fading agent is used for the purpose of improving the storability of images. As the antifading agent, various organic and metal complex antifading agents can be used. Organic compounds include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of metal complexes 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 agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocyclics, and the like. .

The colored dispersion can contain water. The water that can be used is preferably ion-exchanged water, distilled water, or other water containing few impurities. Further, the above colored dispersion can be subjected to precision filtration using a membrane filter or the like. When the above-mentioned colored dispersion is used as an inkjet textile printing ink, it is preferable to carry out microfiltration for the purpose of preventing clogging of nozzles. The pore size of the filter used for microfiltration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

The colored dispersion preferably contains at least one selected from the group consisting of preservatives, surfactants, and pH adjusters as the additive.

The colored dispersion may further contain a resin emulsion.

Examples of the resin emulsion include acrylic resins, epoxy resins, urethane resins, styrene-butadiene resins, polyether resins, polyamide resins, unsaturated polyester resins, phenol resins, silicone resins, fluorine resins, polyvinyl resins (eg, vinyl chloride, vinyl acetate, polyvinyl alcohol, etc.), alkyd resins, polyester resins, or emulsions formed from amino materials (melanin resins, urea resins, urea resins, melanin formaldehyde resins, etc.). Also, these emulsions may be composed of two or more resins. Further, it may be a composite resin in which two or more resins form a core/shell structure. Among these resin emulsions, urethane resins are preferred for use in the above colored dispersion.

The above urethane resins are often sold in the form of latex (emulsion), most of which are emulsions with a solid content of 30 to 60%. Specific examples thereof include, for example, Permaline UA-150, 200, 310, 368, 3945, Yukote UX-320 (manufactured by Sanyo Kasei Co., Ltd.), Hydran WLS-201, 210, latex of HW-312B (above, DIC Corporation), Superflex 150, 170, 470 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and the like. Among these, polycarbonate-based urethane resins include, for example, Permaline UA-310, 3945, Ukote UX-320, and the like. Among these, polyether-based urethane resins include, for example, Permalin UA-150, 200, Ukote UX-340, and the like. 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 (cal/cm ³ ) ^1/2 , more preferably 8 to 17 (cal/cm ³ ) ^1/2 , 11 is particularly preferred. The SP value of urethane resin is calculated by the Fedors method. In addition, when the resin in the urethane resin emulsion has an acidic group and the emulsion is produced by neutralizing the acidic group, the SP value of the resin before neutralization is used.

When the above urethane resin emulsion has acidic groups such as carboxylic acid, sulfonic acid and hydroxyl groups, these acidic groups may be alkali chlorided. Alkali salification can be carried out, for example, by the following method. For example, a urethane resin emulsion having an acidic group is poured into water and stirred to prepare an aqueous solution, and an alkaline compound is added to the aqueous solution to prepare a solution adjusted to pH 6.0 to 12.0.

Examples of the alkaline compound include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide and strontium hydroxide. Hydroxide, triethylamine, and the like can be mentioned. Any one of these alkaline compounds may be used alone, or two or more of them may be used in combination.

The compound represented by the above formula (1) may be a powdery or lumpy dry colorant, a wet cake or a slurry. may be contained in a small amount.

A colored dispersion set containing the above colored dispersion and a colored dispersion having a hue different from that of the colored dispersion is also included in the present invention. The present invention also includes a printing method using a recording medium to which at least one of the compound represented by the above formula (1) and the above-described colored dispersion is adhered, the above-described colored dispersion, or the above-described colored dispersion set.

Examples of the method for preparing the colored dispersion include a method of mixing each of the constituent elements described above. The order in which each component is mixed is not particularly limited.

From the viewpoint of ejection response at high speed, the above-mentioned colored dispersion liquid preferably has a viscosity at 25° C. that is usually about 3 to 20 mPa·s when measured with an E-type viscometer. Further, the surface tension is preferably in the range of 20 to 45 mN/m when measured by the plate method. These values are preferably adjusted to appropriate values in consideration of the ejection volume, response speed, flying characteristics of the dispersed colored droplets, and the like of the printer used.

The printing methods for the hydrophobic fibers are roughly classified into two types. The first method is a method called direct printing or direct textile printing, in which droplets of the colored dispersion are attached to hydrophobic fibers by an inkjet printer to form images such as letters and patterns. Step A of forming information on a hydrophobic fiber, Step B of fixing the sublimable dye in the droplets of the colored dispersion adhered in the step A to the fiber by heat, and Sublimation of the unfixed remaining in the fiber. A method for printing a hydrophobic fiber, comprising at least three steps, a step C of washing the polar dye. Step B is generally performed by known steaming or baking. As steaming, for example, a high temperature steamer is usually used at 170 to 180°C for usually about 10 minutes; a high pressure steamer is usually used for about 20 minutes at usually 120 to 130°C; A method of dyeing the fibers (also called wet heat fixation) can be mentioned. As baking (thermosol), for example, the sublimation dye is dyed on the fiber by a method of treating hydrophobic fiber at usually 190 ° C. to 210 ° C. and usually about 60 seconds to 120 seconds (also called dry heat fixation). method. Step C is a step of washing the obtained fibers with warm water and, if necessary, water. Warm water or water used for washing may contain a surfactant. It is also preferable to dry the washed fibers usually at 50 to 120° C. for 5 to 30 minutes. The second method is a method called sublimation transfer printing, sublimation transfer textile printing, etc., in which droplets of the above-mentioned colored dispersion or a set of colored dispersions are deposited on an intermediate recording medium by an ink-jet printer. After obtaining a recorded image such as characters and patterns, a hydrophobic fiber is brought into contact with the surface of the intermediate recording medium on which droplets of the colored dispersion are adhered, and heat treatment is performed to obtain characters recorded on the intermediate recording medium. , a printing method for hydrophobic fibers in which a recorded image such as a design is transferred to the hydrophobic fibers. As the intermediate recording medium, the sublimable dye in the colored dispersion adhering 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. is preferred. An example of such an intermediate recording medium is paper on which a colored dispersion-receiving layer is formed with inorganic fine particles such as silica. Dry heat treatment at about 190 to 200° C. is usually used as the heat treatment for transferring the recorded image from the intermediate recording medium to the hydrophobic fiber.

The textile printing method may further include a fiber pretreatment step for the purpose of preventing bleeding and the like. This pretreatment step includes applying an aqueous solution containing at least one or more sizing agents, alkaline substances, anti-reduction agents and hydrotropic agents to the fibers prior to application of the colored dispersion. As the pretreatment step, it is preferable to use an aqueous solution of a pretreatment agent containing a sizing agent, an alkaline substance, an anti-reduction agent and a hydrotropic agent as the pretreatment liquid, and impregnate the fibers with the pretreatment liquid. Examples of the sizing agent include natural gums such as guar and locust bean, starches, sodium alginate, seaweed such as funori, plant skins such as pectic acid, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and the like. cellulose derivatives, modified starches such as carboxymethyl starch, and synthetic pastes such as polyvinyl alcohol and polyacrylic acid esters. Sodium alginate is preferred.

Examples of the alkaline substance include alkali metal salts of inorganic acids or organic acids, salts of alkaline earth metals, and compounds that release alkali when heated. Metal salts are preferred, including sodium compounds and potassium compounds. Specific examples include alkali metal hydroxides such as sodium hydroxide and calcium hydroxide, 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. As the anti-reduction agent, sodium meta-nitrobenzenesulfonate is preferred. Examples of the hydrotropic agent include ureas such as urea and dimethylurea, and preferably urea. A single compound may be used for each of the adhesive, alkaline substance, anti-reducing agent, and hydrotropic agent, or a plurality of compounds may be used in combination. The mixing ratio of each pretreatment agent in the total weight of the pretreatment liquid is, for example, 0.5 to 5% of paste agent, 0.5 to 5% of sodium hydrogen carbonate, and metanitrobenzenesulfonic acid, all based on mass. 0-5% sodium, 1-20% urea, balance water. The application of the pretreatment agent to the cellulosic fibers includes, for example, a padding method. The padding reduction rate is preferably about 40 to 90%, more preferably about 60 to 80%.

The above recording media are roughly classified into those having a colored dispersion receiving layer and those not having a colored dispersion receiving layer. Any of these is preferable as the recording medium used in the ink jet recording method. Specific recording media include, for example, paper, film, fibers and cloth (polyester, cellulose, nylon, wool, etc.), leather, color filter substrates, and the like. The colored dispersion-receiving layer is provided on the recording medium for the purpose of absorbing the colored dispersion and hastening its drying. The colored dispersion-receiving layer is formed, for example, by impregnating or coating the above-described recording medium with a cationic polymer; Installed by a method of coating on the surface of the media; Examples of the inorganic fine particles capable of absorbing the dye in the colored dispersion include porous silica, alumina sol, special ceramics, and the like. A recording medium having such a colored dispersion-liquid-receiving layer is usually referred to as dedicated inkjet paper, dedicated inkjet film, glossy paper, glossy film, and the like. Commercially available ink-jet paper includes, for example, Professional Photo Paper (trade name) manufactured by Canon Inc. Moreover, plain paper etc. are mentioned as paper which does not have a colored dispersion receiving layer. Commercially available plain paper includes, for example, plain paper copy (PPC) paper.

The above-mentioned colored dispersion liquid can also be used for recording extremely well on fibers of the above-mentioned recording media. The type of fiber is not particularly limited, but hydrophobic fibers are preferred. Hydrophobic fibers include, for example, polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, polyamide fibers, and blended fibers using two or more of these fibers. In addition, these fibers and regenerated fibers such as rayon; and blended fibers of these fibers with natural fibers such as cotton, silk, and wool are also included in the hydrophobic fibers herein, polyester fibers or Blended fibers containing polyester fibers are preferred.
Some fibers are known to have a colored dispersion-receiving layer, and such fibers can also be used favorably. Fibers having a colored dispersion-receiving layer can be prepared by known methods or obtained commercially. The material, structure, etc. of the colored dispersion-liquid-receiving layer are not particularly limited, and can be used appropriately according to the purpose.

The method of attaching the above-mentioned colored dispersion liquid to a recording medium is not particularly limited, and all known methods (for example, various writing implements, inkjet recording, etc.) can be used. When fibers are used as a recording medium, a surface coating dyeing method including a size press method, a coating method, or an internal dyeing method can be used. In addition, since the above compounds have sublimation properties, a sublimation transfer dyeing method can also be preferably used.

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 hydrophobic fibers in the present specification. Some of these hydrophobic fibers are known to have a colored dispersion receiving layer (anti-bleeding layer), and methods for forming a colored dispersion receiving layer containing such hydrophobic fibers are known techniques. and fibers with colored dispersion-receiving layers are also available commercially. The material, structure, and the like of the colored dispersion-receiving layer are not particularly limited, and can be appropriately used depending on the purpose. Dyed hydrophobic fibers obtained by the above method for printing hydrophobic fibers are also included in the present invention.

The colored dispersion can be used in various fields, and is suitable for water-based writing ink, water-based printing ink, information recording ink, textile printing, etc., and is particularly preferably used as inkjet textile printing ink.

The colored dispersion of the present invention is excellent in storage stability without precipitation of solids, change in physical properties, change in color, etc. after long-term storage. In addition, the ink-jet printer head has good initial filling properties and good continuous printing stability. Furthermore, it is possible to obtain a clear image without blurring of the image on the paper after printing. In addition to these, a dyed article dyed with the coloring dispersion of the present invention has a high dyeing density, is excellent in levelness and light resistance, and has a high-quality black hue. Further, when used in combination with colored dispersions containing yellow, orange, magenta, cyan dyes, etc., it is possible to perform full-color ink-jet printing with excellent fastness and storage stability. As described above, the colored dispersion of the present invention is particularly suitable for use as an inkjet textile printing ink because of its excellent ejection stability. In particular, the value of the dyeing density is a numerical value of 1.39 or more in the following dyeing density evaluation, and in the following dyeability evaluation, yellow bleeding and staining are not seen at the boundary between the dyed part and the white background part, and the boundary is clear. , and the color difference at 60% duty is less than 2.1 in the following color rendering evaluation 1, and the color difference at 60% duty is less than 2.6 in the following color rendering evaluation 2, dyeing It is excellent as a coloring dispersion since it has a high density and gives a black color with excellent dyeability and color rendition, and a better black printed matter can be obtained.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited by the examples. Unless otherwise specified in the examples, "parts" means parts by mass, and "%" means mass%.

[Preparation Example 1]
[Preparation of emulsion liquid]
6 parts of 25% sodium hydroxide, 54 parts of ion-exchanged water, 20 parts of propylene glycol, and 20 parts of Joncryl 678 (manufactured by BASF) are added, heated to 90 to 120 ° C. and stirred for 5 hours to obtain Joncryl 678. was obtained.
[Preparation Example 2]
[Preparation of Y54 dispersion]
30 parts of Kayaset Yellow AG (manufactured by Nippon Kayaku Co., Ltd., CI Disperse Yellow 54) as a sublimation dye, 60 parts of the above Joncryl 678 emulsion, 0.2 parts of Proxel GXL, and 0.4 parts of Surfynol 104PG50 , and 24 parts of ion-exchanged water, was subjected to dispersion treatment for about 15 hours under cooling in a sand mill using 0.2 mm diameter glass beads. After adjusting the dye content to 15% by adding 60 parts of ion-exchanged water and 30 parts of Joncryl 678 emulsion liquid to the obtained liquid, glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size 0.5 μm). Y54 dispersion was obtained by filtration with .
[Preparation Example 3]
[Preparation of Bw27 dispersion]
C.I. I. A mixture of 30 parts of Disperse Brown 27, 60 parts of the above Joncryl 678 emulsion, 0.2 parts of Proxel GXL, 0.4 parts of Surfynol 104PG50, and 24 parts of ion-exchanged water was prepared using 0.2 mm diameter glass beads. In a sand mill, a dispersing treatment was carried out for about 15 hours under cooling. After adjusting the dye content to 15% by adding 60 parts of ion-exchanged water and 30 parts of Joncryl 678 emulsion liquid to the obtained liquid, glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size 0.5 μm). A Bw27 dispersion was obtained by filtration with .
[Preparation Example 4]
[Preparation of B359 dispersion]
C.I. I. A mixture of 30 parts of Disperse Blue 359, 60 parts of the above Joncryl 678 emulsion, 0.2 parts of Proxel GXL, 0.4 parts of Surfynol 104PG50, and 24 parts of ion-exchanged water was prepared using 0.2 mm diameter glass beads. In a sand mill, a dispersing treatment was carried out for about 15 hours under cooling. After adjusting the dye content to 15% by adding 60 parts of ion-exchanged water and 30 parts of Joncryl 678 emulsion liquid to the obtained liquid, glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size 0.5 μm). to obtain a B359 dispersion.
[Preparation Example 5]
[Preparation of B360 dispersion]
C.I. I. A mixture of 30 parts of Disperse Blue 360, 60 parts of the above Joncryl 678 emulsion, 0.2 parts of Proxel GXL, 0.4 parts of Surfynol 104PG50, and 24 parts of ion-exchanged water was prepared using 0.2 mm diameter glass beads. In a sand mill, a dispersing treatment was carried out for about 15 hours under cooling. After adjusting the dye content to 15% by adding 60 parts of ion-exchanged water and 30 parts of Joncryl 678 emulsion liquid to the obtained liquid, glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size 0.5 μm). to obtain a B360 dispersion.
[Preparation Example 6]
[Preparation of R60 dispersion]
30 parts of Kayaset Red B (manufactured by Nippon Kayaku Co., Ltd., CI Disperse Red 60) as a sublimation dye, 60 parts of the above Joncryl 678 emulsion, 0.2 parts of Proxel GXL, and 0.4 parts of Surfynol 104PG50 , and 24 parts of ion-exchanged water, was subjected to dispersion treatment for about 15 hours under cooling in a sand mill using 0.2 mm diameter glass beads. After adjusting the dye content to 15% by adding 60 parts of ion-exchanged water and 30 parts of Joncryl 678 emulsion liquid to the obtained liquid, glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size 0.5 μm). to obtain an R60 dispersion.
[Preparation Example 7]
[Preparation of Or25 dispersion]
C.I. I. A mixture of 30 parts of Disperse Orange 25, 60 parts of the above Joncryl 678 emulsion liquid, 0.2 parts of Proxel GXL, 0.4 parts of Surfynol 104PG50, and 24 parts of ion-exchanged water was prepared using 0.2 mm diameter glass beads. In a sand mill, a dispersing treatment was carried out for about 15 hours under cooling. After adjusting the dye content to 15% by adding 60 parts of ion-exchanged water and 30 parts of Joncryl 678 emulsion liquid to the obtained liquid, glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size 0.5 μm). An Or25 dispersion was obtained by filtration with .
[Preparation Example 8]
[Preparation of Or60 dispersion]
C.I. I. A mixture of 30 parts of Solvent Orange 60, 60 parts of the above Joncryl 678 emulsion, 0.2 parts of Proxel GXL, 0.4 parts of Surfynol 104PG50, and 24 parts of ion-exchanged water was prepared using 0.2 mm diameter glass beads. In a sand mill, a dispersing treatment was carried out for about 15 hours under cooling. After adjusting the dye content to 15% by adding 60 parts of ion-exchanged water and 30 parts of Joncryl 678 emulsion liquid to the obtained liquid, glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size 0.5 μm). An Or60 dispersion was obtained by filtration with .
[Preparation Example 9]
(Step 1) Synthesis of a compound represented by the following formula (13) In 30 parts of DMF, 6.4 parts of m-chloroaniline, 13.8 parts of potassium carbonate, and 8.0 parts of 2-methoxyethyl p-toluenesulfonate were added. In addition, it was heated to 110° C. and reacted for 6 hours. After cooling to 60° C., 100 parts of water was added to the obtained reaction liquid, and extraction was performed three times with 50 parts of toluene. The resulting organic layer was washed three times with 100 parts of 1% aqueous hydrochloric acid and once with 100 parts of water, and then toluene was distilled off using an evaporator to obtain 5.5 parts of an oily substance.
Next, 5.5 parts of the obtained oil, 4.4 parts of potassium carbonate and 7.0 parts of iodoethane were added to 30 parts of DMF, heated to 110° C., and reacted for 6 hours. After cooling to 60° C., 100 parts of water was added to the obtained reaction liquid, and extraction was performed three times with 50 parts of toluene. After washing the resulting organic layer twice with 100 parts of water, toluene was distilled off using an evaporator to obtain 5.5 parts of a compound represented by the following formula (13).

(Step 2) Synthesis of a compound represented by the following formula (14) 8.2 parts of p-nitroaniline and 18.8 parts of 35% hydrochloric acid are added to 50 parts of ice water, and the mixture is heated at 0 to 10°C for 30 minutes. Stirred. At the same temperature, 10.9 parts of 40% sodium nitrite was added and stirred for 1 hour. 10 parts of the compound of formula (13) is added to the resulting reaction solution, and the reaction is carried out at pH 2.0 to pH 2.5 and 0 to 10°C for 2 hours, and then at pH 3.0 to pH 3.5 and 0 to 10°C for 2 hours. carried out. After completion of the reaction, the reaction mixture was filtered and washed with water to obtain 9.3 parts of the compound represented by formula (14).

[Preparation Example 10]
(Step 1) Synthesis of compound represented by the following formula (9) 6.4 parts of m-chloroaniline, 13.8 parts of potassium carbonate and 18.7 parts of iodoethane are added to 30 parts of DMF and heated to 100°C. and reacted for 6 hours. After cooling to 60° C., 100 parts of water was added to the obtained reaction liquid, and extraction was performed three times with 50 parts of toluene. After the obtained organic layer was washed with 100 parts of water three times, the toluene was removed by an evaporator and dried to obtain 10 parts of a compound represented by the following formula (9).

(Step 2) Synthesis of a compound represented by the following formula (10) 8.2 parts of p-nitroaniline and 18.8 parts of 35% hydrochloric acid are added to 50 parts of ice water, and the mixture is heated at 0 to 10°C for 30 minutes. Stirred. At the same temperature, 10.9 parts of 40% sodium nitrite was added and stirred for 1 hour. 10 parts of the compound of formula (9) is added to the resulting reaction solution, and the reaction is carried out at pH 2.0 to pH 2.5 and 0 to 10°C for 2 hours, and then at pH 3.0 to pH 3.5 and 0 to 10°C for 2 hours. carried out. After completion of the reaction, the reaction mixture was filtered and washed with water to obtain 15.0 parts of the compound represented by formula (10).

[Preparation Example 11]
(Step 1) Synthesis of a compound represented by the following formula (11) 8.6 parts of m-bromoaniline, 13.8 parts of potassium carbonate, and 18.7 parts of iodoethane are added to 30 parts of DMF and heated to 100°C. and reacted for 6 hours. After cooling to 60° C., 100 parts of water was added to the obtained reaction liquid, and extraction was performed three times with 50 parts of toluene. After the obtained organic layer was washed with 100 parts of water three times, the toluene was removed by an evaporator and dried to obtain 11 parts of a compound represented by the following formula (11).

(Step 2) Synthesis of a compound represented by the following formula (12) 8.2 parts of p-nitroaniline and 18.8 parts of 35% hydrochloric acid are added to 50 parts of ice water, and the mixture is heated at 0 to 10°C for 30 minutes. Stirred. At the same temperature, 10.9 parts of 40% sodium nitrite was added and stirred for 1 hour. 11 parts of the compound of formula (11) is added to the resulting reaction solution, and the reaction is carried out at pH 2.0 to pH 2.5 and 0 to 10°C for 2 hours, and then at pH 3.0 to pH 3.5 and 0 to 10°C for 2 hours. carried out. After completion of the reaction, the reaction mixture was filtered and washed with water to obtain 14.0 parts of the compound represented by formula (12).

[Preparation Example 12]
(Step 1) Synthesis of Compound Represented by Formula (21) 12.7 parts of m-chloroaniline and 10.6 parts of triethylamine were added to 30 parts of acetone and stirred for 30 minutes. 14.8 parts of benzoyl chloride was added dropwise to this liquid at 40° C. or lower, and the mixture was reacted at 30 to 40° C. for 1 hour. The reaction solution was added dropwise to 700 parts of ice water, filtered, and washed with water to obtain 34.6 parts of the compound of formula (21) as a wet cake. The obtained wet cake was dried to obtain 22.6 parts of the compound of formula (21).

(Step 2) Synthesis of compound represented by the following formula (22) 22.6 parts of the compound of formula (21) was added to 90 parts of dehydrated THF and stirred for 30 minutes. To this solution, 140 parts of a borane-THF complex (0.93 mol/l) was added dropwise over 1 hour at 30°C or lower, and the mixture was reacted at 30-40°C for 1 hour and at 50-60°C for 4 hours. 30 parts of water was added dropwise to the reaction liquid over 1 hour, and the mixture was stirred for 1 hour. By concentrating this reaction solution, 21.2 parts of the compound of formula (22) was obtained.

(Step 3) Synthesis of a compound represented by the following formula (23) To 70 parts of DMF, 21.2 parts of the compound of formula (22), 22.7 parts of potassium carbonate, and 34.7 parts of iodoethane were added, and the temperature was adjusted to 100°C. and reacted for 6 hours. After cooling to 60° C., 250 parts of water was added to the obtained reaction liquid, and extraction was performed three times with 200 parts of toluene. After the obtained organic layer was washed with 200 parts of water three times, the toluene was removed by an evaporator and dried to obtain 24.7 parts of a compound represented by the following formula (23).

(Step 4)
Synthesis of Compound Represented by Formula (24) 8.2 parts of p-nitroaniline and 18.8 parts of 35% hydrochloric acid were added to 50 parts of ice water, and the mixture was stirred at 0 to 10° C. for 30 minutes. At the same temperature, 10.9 parts of 40% sodium nitrite was added and stirred for 1 hour. 12.3 parts of the compound of formula (23) is added to the resulting reaction solution, and the mixture is stirred at pH 2.0 to pH 2.5 at 0 to 10°C for 2 hours and at pH 3.0 to pH 3.5 at 0 to 10°C for 2 hours. The reaction was carried out. After completion of the reaction, the reaction mixture was filtered and washed with water to obtain 14.7 parts of the compound represented by formula (24).

[Example 1]
[Preparation of Colored Dispersion 1]
15 parts of the compound represented by the above formula (14), 4.5 parts of TS-1500, 4.5 parts of SM-57, 0.1 parts of Proxel GXL, 0.2 parts of Surfynol 104PG50, ion exchange A mixture of 75.7 parts of water was subjected to dispersion treatment using 0.2 mm diameter glass beads in a sand mill under cooling for about 15 hours. A colored dispersion 1 was obtained by filtering through a glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size 0.5 μm).
[Examples 2-7, Comparative Examples 1-2]
[Preparation of colored dispersions 2 to 9]
Colored dispersions 2 to 9 were obtained in the same manner as in Example 1 except that the type and amount of the compound represented by the above formula (1) as shown in Table 1 and the amount of the dispersant were changed.
The abbreviations in Table 1 below represent the following, respectively.
TS-1500: Polyoxyethylene arylphenyl ether dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
SM-57: Polyoxyethylene arylphenyl ether sulfate-based dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
JC678: Joncryl 678 (manufactured by BASF Japan Ltd.)

[Ink preparation]
[Example 8]
6 parts of the Y54 dispersion obtained in Preparation Example 3 above, 25 parts of the colored dispersion 1 obtained in Example 1 above, 6 parts of the B359 dispersion obtained in Preparation Example 2 above, and B360 obtained in Preparation Example 5 18 parts of dispersion liquid 8 are mixed, 15 parts of glycerin, 10 parts of propylene glycol, 0.1 part of Proxel GXL (manufactured by Lonza), 0.8 parts of BYK-348 (manufactured by BYK Chemie Japan), 0.1 part of TEA-80 (manufactured by Junsei Chemical Co., Ltd.), 5.0 parts of methoxy glycol, and 14.0 parts of ion-exchanged water were added and stirred, followed by filtration through a 5 μm filter. Ink 1 was obtained.
[Examples 9 to 14, Comparative Examples 3 to 7]
Inks 2 to 12 were obtained in the same manner as in Example 8, except that the type and amount of the colored dispersion and the amount of ion-exchanged water shown in Table 2 were changed.

Using each of the colored dispersions and inks prepared as described above, the following evaluation tests were carried out. The results are shown in Tables 1 and 2 above.

[Intermediate recording medium printed with ink and sublimation transfer textile printing using it]
Each prepared ink is filled in an inkjet printer (manufactured by EPSON Corporation, trade name PX-504A), and TRANSJET Eco II 8385 (95 g/m ² ) is used as an intermediate recording medium to print at 100% Duty or 25% Duty. An intermediate recording medium on which a single-color solid image was printed was obtained. After superimposing the ink adhering surface of each obtained intermediate recording medium and a polyester cloth (Teijin Tropical), using a tabletop automatic flat press machine (manufactured by Asahi Textile Machinery Co., Ltd.: AF-65TEN) 200 ° C. × 30 seconds. Dyed products dyed by the sublimation transfer dyeing method were obtained by heat treatment under the conditions of . Each dyed product obtained was evaluated as follows.

[Color rendering property 1: color difference between D65 light source and F2 light source]
Using a spectrophotometer “eXact (manufactured by X-rite)”, heat treatment under the conditions of 200 ° C. × 30 seconds, 25% duty single color solid dyed by sublimation transfer dyeing method Each dyed product The hue L*a*b* of was measured. Colorimetry was performed using a viewing angle of 2° and the conditions of Status I to obtain each L ^* a ^* b ^* value for the D65 light source and the F2 light source. From the obtained L ^* a ^* b ^* values of each light source, the color difference ΔE _D65-F2 was obtained from the following (Equation 1) and evaluated according to the following evaluation criteria.
The evaluation results are shown in Table 2 above.

ΔE _D65-F2 = [(L ^* _D65 -L ^* _F2 ) ²⁺ (a ^* _D65 -a ^* _F2 ) ²⁺ (b ^* _D65 -b ^* _F2 ) ² ] ^1/2 (Equation 1)

[Evaluation criteria]
A: Color difference ΔE _D65-F2 is 1.0 or more and less than 4.5.
B: Color difference ΔE _D65-F2 is 4.5 or more and less than 5.0.
C: Color difference ΔE _D65-F2 is 5.0 or more.

[Color rendering property 2: color difference between D65 light source and A light source]
Using a spectrophotometer “eXact (manufactured by X-rite)”, heat treatment under the conditions of 200 ° C. × 30 seconds, 25% duty single color solid dyed by sublimation transfer dyeing method Each dyed product The hue L*a*b* of was measured. Colorimetry was performed using a viewing angle of 2° and the conditions of status I to obtain each L ^* a ^* b ^* value for the D65 illuminant and the A illuminant. Color difference ΔE _D65-A was obtained from the following (Equation 2) from the L ^* a ^* b ^* values obtained for each light source, and evaluated according to the following evaluation criteria.
The evaluation results are shown in Table 2 above.

ΔE _D65-A = [(L ^* _D65 - L ^* _A ) ² + (a ^* _D65 - a ^* _A ) ² + (b ^* _D65 - b ^* _A ) ² ] ^1/2 (Formula 2)

[Evaluation criteria]
A: Color difference ΔE _D65-A is 1.0 or more and less than 3.5.
B: Color difference ΔE _D65-A is 3.5 or more and less than 4.0.
C: Color difference ΔE _D65-A is 4.0 or more.

[Color development: Sigma K/S value]
Using a spectrophotometer “eXact (manufactured by X-rite)”, heat treatment at 200 ° C. × 30 seconds, 100% duty single color solid dyed by sublimation transfer dyeing method Each dyed product was measured. Colorimetry was performed under the conditions of a D65 light source, a viewing angle of 2°, and status I. The reflectance R lambda at 400-700 nm of each dyed cloth was measured, and the K/S value was calculated by the Kubelka-Munk formula: K/S=(1−R lambda) 2/2 R lambda. Then, the sigma K/S value, which is the sum of the K/S values at each wavelength, was calculated, and the staining density was evaluated according to the following criteria. The higher the Sigma K/S value, the higher the dyeing density and thus the better the quality.
The evaluation results are shown in Table 2 above.
[Evaluation criteria]
A: Sigma K/S value of 470 or more B: Sigma K/S value of 450 or more and less than 470 C: Sigma K/S value of 430 or more and less than 450
[Redispersibility]
25 μL of each of the colored dispersion liquid and the ink of each of the above Examples and Comparative Examples was dropped on a glass petri dish and dried in a constant temperature and humidity machine at 60° C. for 1 hour.
After drying, 10 mL of deionized water was added dropwise at room temperature, and whether redispersion occurred or not was visually observed and evaluated according to the following four-grade criteria.
Inks that can be redispersed with little or no residue are excellent because clogging after drying can be easily eliminated. In the case of A, B or C, the redispersibility was evaluated as good, and in the case of D, it was evaluated as poor. The results are shown in Tables 1 and 2 above.
[Evaluation criteria]
A: All redispersed with no residue.
B: A little residue remains, but most of it is redispersed.
C: A lot of residue remains, but somewhat redispersed.
D: No redispersion at all.

As is clear from the results in Table 2 above, the colored dispersions of Examples 1 to 7 are superior to the colored dispersions of Comparative Examples 1 and 2 in redispersibility. In addition, as is clear from the results in Table 3 above, the inks of Examples 8 to 14 using the colored dispersions of Examples 1 to 7 had excellent redispersibility compared to the inks of Comparative Examples 3 to 7. In addition, the color rendering and color development properties are high, and it can be seen that a high-quality black color is exhibited. In addition, the colored dispersion containing the dye represented by the formula (1) according to the present invention has high transfer efficiency and gives a dyed product with a high dyeing density and an excellent color tone. This indicates that it is extremely useful as a textile printing ink.

The colored dispersion of the present invention has excellent redispersibility, high sublimation transfer efficiency, and high dyeing density. In addition, it is extremely useful as a black ink for sublimation transfer inkjet textile printing because it is possible to obtain dyed products with excellent color rendering properties and maintain the printability required for various textile printing inks, especially inkjet textile printing inks. be.

Claims (8)

(A) a compound represented by the following formula (1), (B) a polyoxyethylene arylphenyl ether-based dispersant and a polyoxyethylene arylphenyl ether sulfate-based dispersant, and a yellow dye dissolved in acetone. One type of blue dye having a maximum absorption wavelength in the wavelength region of 620 nm or more and less than 700 nm in the ultraviolet-visible spectral absorption of the solution dissolved in acetone, and the ultraviolet-visible spectral absorption of the solution dissolved in acetone has a maximum in the wavelength region of 550 nm or more and less than 620 nm. A colored dispersion containing one type of blue dye having an absorption wavelength .

(In formula (1), R ¹ represents a hydrogen atom or a nitro group. R ² and R ³ each independently represents a C1-C4 alkyl group optionally substituted with a C1-C4 alkoxy group or a phenyl group. ^.R4 represents a halogen atom.In addition, ^R2 and ^R3 may be linked to each other to form a ring.) 2. The colored dispersion according to claim 1, wherein ^R4 in formula (1) above is a chlorine atom or a bromine atom. Claim 1, wherein R ¹ in the above formula (1) is a hydrogen atom, R ² and R ³ are each independently a C1-C4 alkyl group optionally substituted with a C1-C4 alkoxy group, and R ⁴ is a chlorine atom. The colored dispersion described in . The colored dispersion according to any one of claims 1 to 3, further comprising a water-soluble organic solvent. A recording medium to which the colored dispersion according to any one of claims 1 to 4 is adhered. 6. A recording medium according to claim 5 , wherein said recording medium is a fiber. 7. A recording medium according to claim 6 , wherein said fibers are hydrophobic fibers. 8. The recording medium according to claim 7 , wherein the hydrophobic fiber is a polyester or a blended fiber containing polyester.