JP7417430B2 - A colored dispersion, an ink composition using the same, a method for improving dispersion stability using the same, and a method for printing hydrophobic fibers. - Google Patents

Description

(A) a compound represented by the following formula (1), (B) C.I. I. Disperse Blue 360 contains (C) a dispersant, and when the total content of (A) and (B) is 100, the content of (B) is 10 or more and 90 or less, and (C) the dispersant is A colored dispersion containing at least one selected from the group consisting of a polyoxyethylene arylphenyl ether dispersant and a polyoxyethylene arylphenyl ether sulfate dispersant, and printing of recording media and hydrophobic fibers to which these are attached. Regarding the method.

In recent years, a recording method that performs plateless printing using inkjet has been proposed, and inkjet printing is also used for printing fibers including cloth. Compared to conventional textile printing methods such as screen printing, inkjet printing has various advantages such as no plate making, resource saving, energy saving, and ease of high-definition expression. There are advantages. Here, hydrophobic fiber cloth such as polyester fiber is generally dyed with a water-insoluble coloring material. Therefore, as an aqueous ink for printing hydrophobic fibers by an inkjet recording method, it is generally necessary to use a dispersion ink in which a water-insoluble coloring material is dispersed in water and has good performance such as dispersion stability. Inkjet printing methods for hydrophobic fibers, typically polyester fibers, can be broadly divided into the following two methods. The direct printing method involves applying ink directly to the fibers (printing) and then dyeing the fibers with the dye in the ink through 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 using heat. This is a sublimation transfer method.

Among the above, the sublimation transfer method is mainly used for printing flags and the like, and the ink uses an easily sublimable dye that has excellent transferability to polyester by heat treatment. As for the processing process,
(1) Printing process: a process of applying dye ink to the intermediate recording medium using an inkjet printer,
(2) Transfer process: process of transferring and dyeing the dye from the intermediate recording medium into the fiber by heat treatment,
Since commercially available transfer paper can be widely used, pretreatment of the fibers is not required, and the washing step is also omitted.

The inkjet ink used in the sublimation transfer method is mainly a water-based ink, in which sublimable dyes selected from water-insoluble disperse dyes and oil-soluble dyes are dispersed and stabilized in fine particles in water using a dispersant. A water-soluble organic solvent is added as a humectant (anti-drying agent), a surfactant is used as a surface tension adjuster, and other additives (pH adjuster, preservative/antifungal agent, antifoaming agent, etc.) are added to this dye dispersion. The ink is made by optimizing the physical properties such as particle size, viscosity, surface tension, and pH using the ink (see Patent Document 1). In addition, in inkjet printing, it is important to be able to stably eject ink from the plate on which the print head nozzles are arranged, but with water-based ink, ejection problems can occur due to evaporation of water in the ink near the nozzle plate. It's easy to happen. The above-mentioned ejection troubles include, for example, when the ink composition adheres to and dries on the plate, it cannot be removed quickly by the printer's cleaning operation, resulting in ink ejection failure (curved flight, etc.) during printing. There are many things that can be mentioned. In order to solve these problems, for example, when expressing black using dyes having sublimation properties, black is usually expressed by combining a plurality of dyes. This is because a single dye alone is not sufficient as a black hue and often has a low density, so by combining multiple dyes, it is possible to express black well. However, when a fabric is dyed with a black ink that combines multiple sublimable dyes, the black color expressed on the fabric may change depending on the type of fabric when the fabric is irradiated with light with a different spectral distribution of the light source. In some cases, the hues appeared to be different colors. For example, under lighting with little long-wavelength light such as fluorescent lighting, good colors may be expressed, but under sunlight with a lot of long-wavelength light, the color may appear reddish, or vice versa. Even if the colors were good under fluorescent lighting, they sometimes appeared bluish under fluorescent lighting. As described above, the characteristics that affect the appearance of colors of objects due to the illumination light source are generally referred to as "color rendering properties," and there has been a demand for black ink that exhibits little change in hue due to the influence of this color rendering properties. Furthermore, inkjet inks are required to have good jetting properties, and if the dye is unstable or poorly dispersed in the ink, the jetting properties in the inkjet head often become unstable. However, black ink in which the types and amounts of sublimable dyes are increased by combining a plurality of dyes has problems in ejection stability and storage stability of the ink.

On the other hand, in the sublimation transfer method for printing hydrophobic fibers, sublimation transfer ink is applied (printed) to an intermediate recording medium (such as a special transfer paper) using an inkjet printer, and the ink-applied (printed) surface of the intermediate recording medium and The objects to be dyed (polyester fibers, etc.) are stacked one on top of the other, and the sublimable dye is transferred onto the objects by a thermocompression method using a thermocompression roller, a heat press, or the like. In commercial printing, inkjet printing is becoming faster and there is a need for inkjet inks to be designed to accommodate higher speeds. In addition, 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 special paper for inkjet printing has a relatively large basis weight so that a large amount of ink can be applied. However, in recent years, transfer papers with smaller basis weights and transfer papers with fewer ink-receiving layers have been used, and there is a strong demand for high transfer efficiency and high dye density with a small amount of ink. In addition, there is a need for a black ink that does not vary in black hue depending on sublimation transfer conditions and has a uniform sublimation speed. Patent Document 2 describes an inkjet black ink used as a disperse dye ink for textile printing, in which the ultraviolet-visible spectral absorption of a water-soluble organic solvent containing glycol ether and a solution dissolved in acetone has a maximum in a certain wavelength range. A black inkjet ink characterized by containing first to fourth disperse dyes having absorption wavelengths is described, but the ink directly applied to pretreated polyester fibers in a direct printing method is mentioned. , there has been no technical study related to dyes with sublimation properties that can be used in the sublimation transfer method, and there is no disclosure of level dyeing properties or dyeing performance in high-density dyeing.

The inkjet ink used in the sublimation transfer method is mainly a water-based ink, in which a dye selected from the water-insoluble disperse dye group and the oil-soluble dye group is stabilized by dispersing fine particles in water using a dispersant. A dispersion liquid is prepared, and a water-soluble organic solvent is used as a humectant (anti-drying agent), a surfactant is used as a surface tension adjuster, and other additives (pH adjuster, preservative/anti-mold agent, antifoaming agent, etc.) are used. Ink has been made by optimizing physical properties such as particle size, viscosity, surface tension, and pH (see Patent Document 1). In addition, in inkjet printing, it is important to be able to stably eject ink from the plate on which the print head nozzles are arranged, but with water-based ink, ejection problems can occur due to evaporation of water in the ink near the nozzle plate. It's easy to happen. The above-mentioned ejection troubles include, for example, when the ink composition adheres to and dries on the plate, it cannot be removed quickly by the printer's cleaning operation, resulting in ink ejection failure (curved flight, etc.) during printing. There are many things that can be mentioned. Inkjet inks are also required to have good jetting properties, and if the dye is unstable or poorly dispersed in the ink, there is a problem that the jetting properties in the inkjet head will become unstable.

WO2005/121263 Patent No. 6191234

The present invention makes it possible to produce dyed products with excellent color rendering properties in sublimation transfer dyeing using inkjet printing, and to obtain high-quality dyed products with high sublimation transfer efficiency and high density dyeing. It is an object of the present invention to provide an inkjet textile printing ink dispersion liquid which can be used as an inkjet textile ink and has good storage stability.

The present inventors have conducted extensive research to solve the above-mentioned problems, and have found that (A) a compound represented by the following formula (1), (B) C.I. I. Disperse Blue 360 contains (C) a dispersant, and when the total content of (A) and (B) is 100, the content of (B) is 10 or more and 90 or less, and (C) the dispersant is It has been discovered that a colored dispersion solution containing at least one selected from the group consisting of a polyoxyethylene arylphenyl ether dispersant and a polyoxyethylene arylphenyl ether sulfate dispersant solves the above problems, This completes the present invention.

That is, the present invention relates to the following 1) to 9).
1)
(A) a compound represented by the following formula (1), (B) C.I. I. Disperse Blue 360 contains (C) a dispersant, and when the total content of (A) and (B) is 100, the content of (B) is 10 or more and 90 or less, and (C) the dispersant is A colored dispersion containing at least one selected from the group consisting of a polyoxyethylene arylphenyl ether dispersant and a polyoxyethylene arylphenyl ether sulfate dispersant.

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

ADVANTAGE OF THE INVENTION According to the present invention, it is possible to produce a dyed product that has excellent storage stability, has little change in hue due to the influence of color rendering properties in sublimation transfer dyeing using inkjet printing, has high sublimation transfer efficiency, and obtains a dyed product with high density. A colored dispersion and an ink that can produce high-quality black dyed products are obtained.

The present invention will be explained in detail below. In this specification, including Examples, unless otherwise specified, all "parts" and "%" are based on mass. Moreover, the content represents the contained mass. Further, in the present specification, the unit indicating the quantitative relationship between (A) and (B) is %. Moreover, in this specification, "C.I." means "color index."

The colored dispersion according to the present invention comprises (A) a compound represented by the following formula (1), (B) C.I. I. Disperse Blue 360 contains (C) a dispersant, and when the total content of (A) and (B) is 100, the content of (B) is 10 or more and 90 or less, and (C) the dispersant is A colored dispersion containing at least one selected from the group consisting of a polyoxyethylene arylphenyl ether dispersant and a polyoxyethylene arylphenyl ether sulfate dispersant.

In formula (1), R ¹ represents a hydrogen atom or a nitro group. R ² and R ³ each independently represent a C1-C4 alkyl group which may be substituted with a C1-C4 alkoxy group or a phenyl group. R ⁴ represents a halogen atom. Further, R ² and R ³ may be connected to each other to form a ring.

The above 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 above C1 to C4 alkyl groups include linear alkyl groups such as methyl group, ethyl group, n-propyl group, and n-butyl group, iso-propyl group, sec-butyl group, and tert-butyl group. Examples include cyclic alkyl groups such as chain alkyl groups and cyclobutyl groups.

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

Examples of the C1-C4 alkyl group substituted with the 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, etc., preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

R ² and R ³ in the above formula (1) may be connected to each other to form a ring. Examples of the ring formed by connecting R ² and R ³ to each other include a piperidine ring, a piperazine ring, a morpholine ring, etc., and it is preferable that they form a piperidine ring.

In the above formula (1), it is preferable that R ¹ is a hydrogen atom, R ² and R ³ are each independently a C1 to C4 alkyl group which may be substituted with a C1 to C4 alkoxy group, and R ⁴ is a chlorine atom; A more preferred combination is that ¹ is a hydrogen atom, R ² and R ³ are each independently an ethyl group which may be substituted with a methoxy group, and R ⁴ is a chlorine atom, R ¹ is a hydrogen atom, and both R ² and R ³ are A combination of a methoxyethyl group, R ⁴ is a chlorine atom, R ¹ is a hydrogen atom, R ² and R ³ are each an ethyl group, and R ⁴ is a chlorine atom, R ¹ is a hydrogen atom, either R ² or R ³ A combination in which one is a methoxyethyl group, the other is an ethyl group, and R ⁴ is a chlorine atom is extremely 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, and R ² and R ³ are connected to each other to form a morpholine ring. to 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 chlorine atom, R ¹ is a hydrogen atom, R ² and R ³ are both ethyl groups, R ⁴ is a bromine atom, 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 preferable 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) using a conventional method, and then combining the obtained diazo compound with the compound represented by the following formula (3). It can be obtained by a coupling reaction using a method. In the following formulas (2) and (3), R ¹ to R ⁴ are the same as in the above formula (1).

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

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

Disperse dyes are classified into blue dyes, cyan dyes, red dyes, yellow dyes, orange dyes, etc. based on their maximum absorption wavelengths. In order to obtain a black 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 is less affected by color rendering properties. be able to. The colored dispersion liquid contains a compound represented by the above formula (1) and C.I. I. By containing a yellow dye and a blue dye in addition to Disperse Blue 360, a colored dispersion having a good black hue can be obtained. In particular, the compound represented by the above formula (1) and C.I. I. In addition to Disperse Blue 360, it contains one type of yellow dye and one type of blue dye that has 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. is preferred.

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

[About blue dye]
The above-mentioned blue dye is not particularly limited as long as it is a dye that generally has a blue hue, but water-insoluble blue dyes are preferred, and among water-insoluble blue dyes, disperse dye blue It is more preferable to use a C.I.-based dye or an oil-soluble blue dye. I. Disperse Blue dye, C.I. I. More preferably, it is a Solvent Blue dye. C. I. Examples of the Disperse Blue dye include 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, 336 and the like. C. I. Examples of Solvent Blue dyes include C.I. I. Examples include Solvent Blue 3, 36, 63, 83, 105, and 111. These dyes can be used alone or in combination. The blue dye mentioned above is C.I. I. Disperse Blue 60, 72, 334, 359 is preferred; I. More preferably, it is Disperse Blue 359. The C. I. Disperse Blue 359 is a blue dye having a maximum absorption wavelength in a wavelength range of 620 nm or more and less than 700 nm in the ultraviolet-visible spectral absorption of a solution dissolved in acetone.

In the colored dispersion, the compound represented by the above formula (1) and the C.I. I. The total content ratio of Disperse Blue 360, the above yellow dye, and the above blue dye can be set arbitrarily, but it is usually set on a mass basis (mass%) with respect to the total mass of the colored dispersion. It is 1 to 20%, preferably 2 to 15%, more preferably 3 to 10%.

[About other dyes that may be included in the colored dispersion]
The colored dispersion liquid contains a compound represented by the above formula (1), C.I. I. In addition to Disperse Blue 360, the above-mentioned yellow dye, and the above-mentioned blue dye, other dyes may be included. Examples of such other dyes include, for example, dye fastness test method for dry heat treatment [JIS L 0879:2005] (confirmed in 2010, revised on January 20, 2005, published by Japan Standards Association), "ISO 105-P01" , Textiles-Tests for color fastness-PartP01: Color fastness to dry heat (excluding pressing)", the test result of heat-sensitive treatment test (Method C) contamination (polyester) is preferably grade 3-4 or lower, more preferably 3 Examples include dyes of grade or lower. Among such known dyes, C.I. I. Examples of dyes with numbers include the following dyes.

Examples of other yellow dyes in the above-mentioned other dyes include C.I. I. Disperse Yellow dye and C.I. I. Solvent yellow dyes other than those exemplified above as yellow dyes may be used. These dyes can be used alone or in combination.

Among the other blue dyes mentioned above, examples of other blue dyes include C.I. I. Disperse Blue dye and C.I. I. Examples of Solvent Blue dyes include those other than those exemplified as the blue dyes above. These dyes can be used alone or in combination.

Examples of other orange dyes in the above-mentioned other dyes include 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; C. I. Examples include Solvent Orange 60 and 67. These dyes can be used alone or in combination.

Other brown dyes among the above-mentioned other dyes include, for example, C.I. I. Disperse Brown 1, 3, 22, 26, 27; and the like. These dyes can be used alone or in combination.

Among the other red dyes mentioned above, examples of other red dyes include 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;C. I. Vat Red 41; and the like. These dyes can be used alone or in combination.

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

Each of the above dyes may be a dry coloring material in the form of a powder or block, or a wet cake or slurry, and a small amount of a dispersant such as a surfactant may be contained in order to suppress the agglomeration of coloring material particles during or after coloring material synthesis. It may be something that Commercially available dyes include grades for industrial dyeing, resin coloring, ink, toner, and inkjet use, and each grade differs in manufacturing method, purity, particle size, etc. In order to suppress agglomeration after pulverization, it is preferable that the coloring material has smaller particles, and in view of the influence on dispersion stability and ink ejection accuracy, it is preferable that it contains as few impurities as possible. As for the dye, it can be used as a coloring material for black by blending a yellow dye, an orange dye, and a red dye mainly with a blue dye. Further, a small amount of other water-insoluble coloring materials may be included within the range of color tone adjustment.

The colored dispersion liquid contains any dispersant selected from the group consisting of a polyoxyethylene arylphenyl ether type dispersant and a polyoxyethylene arylphenyl ether sulfate type dispersant.

Specifically, the polyoxyethylene arylphenyl ether dispersants and polyoxyethylene arylphenyl ether sulfate dispersants mentioned above include polyoxyethylene monostyrylphenyl ether, polyoxyethylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, Styryl phenol compounds such as styryl phenyl ether and polyoxyethylene tetrastyrylphenyl ether, benzyl phenol compounds such as polyoxyethylene monobenzylphenyl ether, polyoxyethylene dibenzylphenyl ether, and polyoxyethylene tribenzylphenyl ether; Examples include cumylphenol compounds such as mylphenyl ether, polyoxyethylene naphthylphenyl ether, polyoxyethylene biphenyl ether, and polyoxyethylene phenoxyphenyl ether. These can be used alone or in combination. Preferred are polyoxyethylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, polyoxyethylene dibenzylphenyl ether, polyoxyethylene tribenzylphenyl ether, and polyoxyethylene cumylphenyl ether. Here, the number b of repeating units of the polyoxyethylene group is an integer of 1 to 30, preferably an integer of 15 to 30. When b is an integer of 1 or more, it has excellent compatibility with the aqueous solvent and other additives, and when it is an integer of 30 or less, the viscosity does not become too high, which is preferable. These are also called arylphenol compounds.

Examples of such arylphenol compounds include those described below. As the styrylphenol compound, commercially available products such as Noigen EA series manufactured by Daiichi Kogyo Seiyaku Co., Ltd. and TS-2000, TS-2600, and SM-174N manufactured by Toho Chemical Industry Co., Ltd. can be used. Further, as the benzylphenol compound, for example, a commercial product such as Emulgen B-66 manufactured by Kao Corporation can be used, and as the cumylphenol compound, for example, a commercial product such as Nucor CMP series manufactured by Nippon Nyukazai Co., Ltd. can be used. can be used.
Examples of polyoxyethylene arylphenyl ether dispersants include Pionin D-6112, Pionin D-6115, Pionin D-6120, Pionin D-6131, Pionin D-6512, Takesurf D-6413, DTD-51, and Pionin D. -6112, Pionin D-6320 (all manufactured by Takemoto Yushi Co., Ltd.), TS-1500, TS-2000, TS-2600, SM-174N (all manufactured by Toho Chemical Co., Ltd.), Emulgen A60, Emulgen A90, Emulgen A500 (Kao ), and these can be used alone 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. It is.

The colored dispersion liquid may further contain other dispersants in addition to the polyoxyethylene arylphenyl ether dispersant and the polyoxyethylene arylphenyl ether sulfate dispersant.

As the other dispersant mentioned above, it is possible to use, for example, a styrene-(meth)acrylic copolymer, a formalin condensate of aromatic sulfonic acid, or a salt thereof. The styrene-(meth)acrylic copolymer is a copolymer of a styrene monomer and a (meth)acrylic monomer. In this specification, "(meth)acrylic" means "acrylic" and/or "methacrylic". Specific examples of these copolymers include (α-methyl)styrene-acrylic acid copolymer, (α-methyl)styrene-acrylic acid-acrylic acid ester copolymer, and (α-methyl)styrene-methacrylic acid copolymer. Polymer, (α-methyl)styrene-methacrylic acid-acrylic ester copolymer, (α-methyl)styrene-(anhydrous) maleic acid copolymer, acrylic ester-(anhydrous) maleic acid copolymer, ( α-methyl)styrene-acrylic acid ester-(anhydrous)maleic acid copolymer, acrylic acid ester-allylsulfonic acid ester copolymer, acrylic acid ester-styrene sulfonic acid copolymer, (α-methyl)styrene-methacrylic Examples include 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 compounds containing an aromatic hydrocarbon group are preferred. Note that (α-methyl)styrene is used herein to include α-methylstyrene and styrene. In the colored dispersion, the other dispersant includes at least one dispersant selected from the group consisting of styrene-(meth)acrylic copolymer, formalin condensate of aromatic sulfonic acid, or a salt thereof. Preferably. The content of other dispersants in the colored dispersion is usually 1 to 36%, preferably 1 to 30%, more preferably 1 to 20%, and still more preferably 1 to 15%.

Specific examples of the other dispersants mentioned above 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), but are not limited to these. Note that in this specification, the superscript RTM means a registered trademark.

The weight average molecular weight of the other dispersants mentioned above is preferably from 1,000 to 20,000, more preferably from 2,000 to 19,000, and particularly preferably from 5,000 to 17,000. The weight average molecular weight of the styrene-acrylic acid copolymer is measured by GPC (gel permeation chromatography). Furthermore, the acid value of the styrene-(meth)acrylic copolymer used as a dispersant is preferably 50 to 250 mgKOH/g, more preferably 100 to 250 mgKOH/g, particularly 150 to 250 mgKOH/g. preferable. If the acid value becomes too low, the solubility of the resin in water will deteriorate, and especially if the colorant is a dispersive dye, the dispersion stabilizing power will tend to be poor, and if the acid value becomes too large, the compatibility with the aqueous medium will decrease. This is undesirable because it tends to make the printed image more prone to 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 transition temperature of the styrene-(meth)acrylic copolymer used as a dispersant is preferably 45°C to 135°C, more preferably 55°C to 120°C, particularly preferably 60°C to 110°C.

Specific examples of styrene-(meth)acrylic copolymers which are other preferable dispersants in the colored dispersion include Joncryl 67 (weight average molecular weight = 12,500, acid value = 213 mgKOH/g), 678 (weight average molecular weight = 12,500, acid value = 213 mgKOH/g), 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 preferred.

The above-mentioned colored dispersion liquid includes the above-mentioned dispersant when dispersing or dissolving the compound represented by the above formula (1), Disperse Blue 360, the above-mentioned yellow dye optionally included, the above-mentioned blue dye optionally containing, and the above-mentioned other dyes. In addition to styrene-acrylic copolymers, two or more types of styrene-acrylic copolymers can be used.

Dispersion of the compound represented by the above formula (1), Disperse Blue 360, the optionally included yellow dye, the optionally included blue dye, and other dyes can be performed, for example, by the following method. The styrene-acrylic copolymer was added to a water-soluble organic solvent and the temperature was raised to 90-120°C to prepare a styrene-acrylic copolymer solution, and an alkaline compound and water were added thereto. to obtain an emulsified (emulsion or microemulsion) liquid, and the prepared emulsion liquid and the compound represented by the above formula (1), Disperse Blue 360, the optionally included yellow dye, the optionally included blue dye, Mix and disperse other dyes.

The formalin condensate of aromatic sulfonic acid or its salt is an anionic surfactant obtained by a condensation reaction of aromatic sulfonic acid and formalin. Examples of "salts thereof" include salts such as sodium salts, potassium salts, and lithium salts. The above-mentioned 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, unless otherwise specified, when described as "formalin condensate of sulfonic acid") , ``salts thereof, or mixtures thereof'') are preferred. For example, creosote oil sulfonic acid, cresol sulfonic acid, phenolsulfonic 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. For example, Demol N is a formalin condensate of β-naphthalene sulfonic acid, Demol C is a formalin condensate of creosote oil sulfonic acid, and Demol SN-B is a formalin condensate of special aromatic sulfonic acid (both are (manufactured by Kao Corporation); and the like. Examples of the formalin condensate of creosote oil sulfonic acid include the Lavelin W series, and examples of the formalin condensate of methylnaphthalene sulfonic acid include the Lavelin AN series (both manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Among these, Demol N, Lavelin AN series, and Lavelin W series are preferred, Demol N and Lavelin W are more preferred, and Lavelin W is even more preferred. Examples of the lignin sulfonic acid include Vanillex N, Vanillex RN, Vanillex G, and Pearlex DP (all manufactured by Nippon Paper Industries Co., Ltd.). Among these, Vanillex RN, Vanillex N, and Vanillex G are preferred.

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

Examples of the water-soluble organic solvent include glycol solvents, polyhydric alcohols, and pyrrolidones. Examples of glycol solvents include glycerin, polyglycerin (#310, #750, #800), diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, and Examples 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 polyC2 polyhydric alcohols having 4 or more repeating units and a molecular weight of about 20,000 or less. -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, 1,5-pentanediol, Examples include 2-pyrrolidone and N-methyl-2-pyrrolidone, and preferably contain at least either glycerin or diglycerin. Further, for convenience, compounds that dissolve in water and serve as wetting agents are included in the water-soluble organic solvent in the present invention, such as urea, ethylene urea, sugars, and the like. Considering storage stability, when the colorant is a disperse dye or an oil-soluble dye, a solvent in which the colorant has a low solubility is preferable, and among these, glycerin and a solvent other than glycerin (preferably a polyhydric alcohol other than glycerin) are preferable. It is preferable to use them together. The total content of the water-soluble organic solvent in the total mass of the colored dispersion is 5 to 50%, preferably 10 to 40%.

The colored dispersion liquid may further contain an additive.

Examples of the additives include preservatives, surfactants, pH adjusters, chelating reagents, rust preventives, water-soluble ultraviolet absorbers, water-soluble polymer compounds, viscosity modifiers, dye solubilizers, anti-fading agents, Examples include antioxidants and water.

Examples of the above-mentioned preservatives include organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, haloallylsulfone-based, iodopropargyl-based, N-haloalkylthio-based, nitrile-based, pyridine-based, 8-oxyquinoline-based, benzo Thiazole series, isothiazoline series, dithiol series, pyridine oxide series, nitropropane series, organotin series, phenol series, quaternary ammonium salt series, triazine series, thiazine series, anilide series, adamantane series, dithiocarbamate series, brominated indanone series , benzyl bromoacetate type, and inorganic salt type compounds. Specific examples of organic halogen compounds include sodium pentachlorophenol, specific examples of pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide, and specific examples of isothiazoline compounds include 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 preservatives and antifungal agents include anhydrous sodium acetate, sodium sorbate, or sodium benzoate, manufactured by Arch Chemical Co., Ltd., trade names Proxel ^RTM GXL (S) and Proxel ^RTM XL-2 (S).

Examples of the surfactant include known surfactants such as anionic, cationic, nonionic, and silicone surfactants. Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acylamino acids and their salts, N-acylmethyl taurine salts, and 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, Examples include diethyl sulfosuccinate, diethylhexyl sulfosuccinate, dioctyl sulfosuccinate, and the like. Specific examples of commercially available products include Hitenol LA-10, LA-12, LA-16, Neo Hitenol ECL-30S, and ECL-45, all manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives. Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, imidazoline derivatives, etc. can be mentioned. Examples of nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether; Ester systems 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) type products such as Nissin Kagaku Co., Ltd., trade name Surfynol 104, 105, 82, 465, Olfine STG, etc.; Polyglycol ether type (e.g. Tergitol 15-S-7, manufactured by SIGMA-ALDRICH Co., Ltd.) ); etc.

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

As the pH adjuster, any substance can be used as long as it can control the pH of the solution within the range of approximately 5 to 11 without adversely affecting the colored dispersion being prepared. Specific examples include alkanolamines such as diethanolamine, triethanolamine, and N-methyldiethanolamine; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonium hydroxide (aqueous ammonia); ; carbonates of alkali metals such as lithium carbonate, sodium carbonate, sodium bicarbonate, 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 above-mentioned chelating reagents include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracildiacetate.

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

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

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

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

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

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

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

The colored dispersion liquid may contain water. The water that can be used is preferably one containing few impurities, such as ion-exchanged water or distilled water. Further, the colored dispersion liquid may be subjected to precision filtration using a membrane filter or the like. When the colored dispersion is used as an inkjet textile ink, it is preferable to perform precision filtration in order to prevent nozzle clogging. The pore size of the filter used for precision filtration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

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 liquid may further contain a resin emulsion.

Examples of the resin emulsions include acrylic resins, epoxy resins, urethane resins, styrene-butadiene resins, polyether resins, polyamide resins, unsaturated polyester resins, phenolic resins, silicone resins, fluororesins, polyvinyl resins (e.g. vinyl chloride, There are emulsions formed from vinyl acetate, polyvinyl alcohol, etc.), alkyd resins, polyester resins, or amino materials (melanin resins, urea resins, urea resins, melanin formaldehyde resins, etc.). Further, these emulsions may be composed of two or more kinds of resins. Furthermore, 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 colored dispersion.

The above-mentioned urethane resin is often sold in the form of latex (emulsion), and most of these are emulsions with a solid content of 30 to 60%. Specific examples include Permarine UA-150, 200, 310, 368, 3945, Ucoat UX-320 (manufactured by Sanyo Chemical Co., Ltd.), Hydran WLS-201, 210, HW-312B latex (all of the above, (manufactured by DIC Corporation), Superflex 150, 170, 470 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and the like. Among these, examples of polycarbonate-based urethane resins include Permarin UA-310, 3945, and Ucoat UX-320. Among these, examples of the polyether urethane resin include Permarin UA-150, UA-200, Ucoat 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, and more preferably 8 to 24 (cal/cm 3 ) ^1/2 . 11 is particularly preferred. Note that the SP value of the urethane resin is calculated by the Fedors method. Furthermore, if the resin in the urethane resin emulsion has acidic groups and the emulsion is prepared by neutralizing these acidic groups, the SP value of the resin before neutralization is used.

When the urethane resin emulsion has acidic groups such as carboxylic acid, sulfonic acid, and hydroxyl groups, these acidic groups may be converted into alkali salts. Alkali chlorination can be carried out, for example, by the following method. Examples include a method in which 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 liquid whose pH is adjusted to 6.0 to 12.0.

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

The compound represented by the above formula (1) may be a dry coloring material in the form of a powder or block, or a wet cake or slurry, and a dispersant such as a surfactant may be used to suppress particle aggregation during or after compound synthesis. It may also contain a small amount of.

A colored dispersion set including the above colored dispersion and a colored dispersion having a hue different from the colored dispersion is also included in the present invention. The present invention also includes a recording medium to which the compound represented by the above formula (1) and Disperse Blue 360 or at least one of the above-mentioned colored dispersion is attached, and a printing method using the above-mentioned colored dispersion or the above-mentioned colored dispersion set. include.

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

The colored dispersion liquid preferably has a viscosity at 25° C. of usually about 3 to 20 mPa·s when measured with an E-type viscometer from the viewpoint of high-speed discharge response. Further, the surface tension is preferably in the range of usually 20 to 45 mN/m when measured by a plate method. It is preferable that each of these values is adjusted to an appropriate value, taking into consideration the ejection amount, response speed, flight characteristics of colored dispersed droplets, etc. of the printer used.

The above-mentioned printing methods for hydrophobic fibers are roughly divided into two types. The first method is called direct printing or direct textile printing, in which droplets of the colored dispersion liquid are attached to hydrophobic fibers using an inkjet printer to create images such as letters and designs. Step A of forming information on hydrophobic fibers, Step B of fixing the sublimable dye in the droplets of the colored dispersion deposited in step A to the fibers by heat, and sublimation of unfixed dyes remaining in the fibers. This is a method for printing hydrophobic fibers, which includes at least three steps: a step C of washing a hydrophobic dye; Step B is generally performed by known steaming or baking. For example, steaming can be carried out using a high-temperature steamer, usually at 170 to 180 degrees Celsius, usually for about 10 minutes; or using a high-pressure steamer, usually at 120 to 130 degrees Celsius, usually for about 20 minutes; An example is a method of dyeing fibers (also called wet heat fixation). Baking (thermosol) involves dyeing the fibers with a sublimable dye using a method that treats hydrophobic fibers, for example, usually at 190°C to 210°C, usually for about 60 to 120 seconds (also called dry heat fixation). There are several methods. Step C is a step of washing the obtained fibers with warm water and, if necessary, with water. The hot water or water used for cleaning 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 printing, etc., in which droplets of the colored dispersion liquid or a set of colored dispersion liquids are attached to an intermediate recording medium using an inkjet printer. After obtaining recorded images such as characters and patterns, hydrophobic fibers are brought into contact with the surface of the intermediate recording medium on which the droplets of the colored dispersion are attached and heat-treated to produce the characters recorded on the intermediate recording medium. This is a printing method for hydrophobic fibers in which a recorded image such as a pattern is transferred onto hydrophobic fibers. The intermediate recording medium is one in which 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 transferring the recorded image to the hydrophobic fiber. is preferred. An example of such an intermediate recording medium is paper on the surface of which a colored dispersion receiving layer is formed of inorganic fine particles such as silica, and special paper for inkjet use can be used. The heat treatment used when transferring the recorded image from the intermediate recording medium to the hydrophobic fibers usually includes dry heat treatment at about 190 to 200°C.

The above-mentioned textile printing method may further include a fiber pretreatment step for the purpose of preventing bleeding and the like. This pretreatment step includes a step of applying an aqueous solution containing at least one type of glue, an alkaline substance, a reduction inhibitor, and a hydrotropic agent to the fibers before the colored dispersion is attached. In the step of applying the pretreatment, it is preferable to use an aqueous solution of a pretreatment agent containing a sizing agent, an alkaline substance, an antireduction agent, and a hydrotropy agent as a pretreatment liquid, and to apply the fibers by impregnating them with the pretreatment liquid. Examples of the above-mentioned thickening agents include natural gums such as guar and locust bean, starches, sodium alginate, seaweeds such as funori, plant skins such as pectic acid, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, etc. Examples include cellulose derivatives, modified starches such as carboxymethyl starch, and synthetic glues such as polyvinyl alcohol and polyacrylic acid esters. Preferred is sodium alginate.

Examples of the alkaline substances include alkali metal salts of inorganic or organic acids, salts of alkaline earth metals, and compounds that liberate alkalis when heated; inorganic or organic alkali metal hydroxides and alkali Metal salts are preferred, including 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 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. Preferred is sodium hydrogen carbonate. As the above-mentioned reduction inhibitor, sodium metanitrobenzenesulfonate is preferable. 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 above-mentioned thickening agent, alkaline substance, reduction inhibitor, and hydrotropic agent, 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% of sizing agent, 0.5 to 5% of sodium bicarbonate, and 0.5 to 5% of metanitrobenzenesulfonic acid, all based on mass. Sodium is 0-5%, urea is 1-20%, and the balance is water. The pretreatment agent may be applied to the cellulose fibers by, for example, a padding method. The aperture ratio of the padding is preferably about 40 to 90%, more preferably about 60 to 80%.

The above-mentioned recording media are roughly divided into those having a colored dispersion receiving layer and those not having a colored dispersion receiving layer. Any of these are preferable as a recording medium used in the inkjet 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 installed on the recording medium for the purpose of absorbing the colored dispersion and hastening its drying. The colored dispersion-receiving layer can be formed, for example, by impregnating or coating the recording medium with a cationic polymer; inorganic fine particles that can absorb the dye in the colored dispersion are used together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone for recording. It is installed by coating the surface of the media; etc. Examples of the inorganic fine particles that can absorb the dye in the colored dispersion include porous silica, alumina sol, and special ceramics. A recording medium having such a colored dispersion receiving layer is usually called inkjet paper, inkjet film, glossy paper, glossy film, or the like. Commercially available inkjet paper includes, for example, Professional Photo Paper manufactured by Canon Inc. and the like. Examples of paper without a colored dispersion receiving layer include plain paper and the like. Commercially available plain paper includes, for example, plain paper copy (PPC) paper.

The above-mentioned colored dispersion liquid can perform recording very suitably even on fibers among the above-mentioned recording media. The type of fiber is not particularly limited, but hydrophobic fibers are preferred. 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 fibers and recycled fibers such as rayon; and blended fibers of these fibers and natural fibers such as cotton, silk, and wool are also included in the hydrophobic fibers in this specification, and polyester fibers or Preferably, it is a blended fiber containing polyester fiber.
Some fibers are known to have a colored dispersion receiving layer, and such fibers can also be suitably used. Fibers having a colored dispersion-receiving layer can be prepared by known methods or can be obtained commercially. The material and structure of the colored dispersion receiving layer are not particularly limited, and can be used as appropriate depending on the purpose.

The method for attaching the colored dispersion liquid to the recording medium is not particularly limited, and all known methods (for example, various writing instruments, inkjet recording, etc.) can be used. When using fibers as a recording medium, a surface coating dyeing method including a size press method, a coating method, or an internal dyeing method can also be used. Further, since the above-mentioned compound has sublimation property, 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 recycled fibers such as rayon, and natural fibers such as cotton, silk, and wool are also included in the hydrophobic fibers in this specification. Among these hydrophobic fibers, those having a colored dispersion receiving layer (bleeding prevention layer) are also known, and such hydrophobic fibers are also included. The method for forming the colored dispersion receiving layer is a known technique, and fibers having the colored dispersion receiving layer are also available as commercial products. The material and structure of the colored dispersion receiving layer are not particularly limited, and can be used as appropriate depending on the purpose. Dyed hydrophobic fibers obtained by the above hydrophobic fiber printing method are also included in the present invention.

The above-mentioned colored dispersion can be used in various fields, but is suitable for aqueous writing inks, aqueous printing inks, information recording inks, textile printing, etc., and is particularly preferably used as an ink for inkjet textile printing.

The colored dispersion of the present invention has excellent storage stability without solid precipitation, physical property changes, color changes, etc. after long-term storage. In addition, the initial filling property into the inkjet printer head is good, and the continuous printing stability is also good. Furthermore, it is possible to obtain a clear image without blurring of the image on the paper after printing. In addition to these, the dyed product dyed with the colored dispersion of the present invention has a high dyeing density, excellent level dyeing properties and light fastness, and has a high-quality black hue. Further, by using the dyes in combination with colored dispersions containing yellow, orange, magenta, cyan dyes, etc., it is possible to perform full-color inkjet printing with excellent fastness and storage stability. As described above, the colored dispersion of the present invention has extremely excellent ejection stability, and is therefore particularly suitable for use in inkjet textile printing inks. In particular, the staining density value is 1.39 or higher in the staining density evaluation below, and in the staining evaluation below, there is no yellow bleeding or staining at the boundary between the dyed area and the white background area, and the boundary area is clear. If the color difference at 60% duty is less than 2.1 in color rendering evaluation 1 below, and the color difference at 60% duty is less than 2.6 in color rendering evaluation 2 below, dyeing It has a high concentration, produces a black color with excellent dyeing properties and color rendering properties, and produces a better black printed product, making it more excellent as a colored dispersion.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by the Examples. In the examples, unless otherwise specified, "part" means part by mass, and "%" means % by mass.
[Preparation example 1]
[Preparation of B360 dispersion]
C. as a sublimable dye. I. A mixture consisting 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 sand milled using 0.2 mm diameter glass beads. The dispersion 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) was added. A B360 dispersion was obtained by filtration.
[Preparation example 2]
[Preparation of B359 dispersion]
A B359 dispersion was obtained in the same manner as in Preparation Example 1, except that the sublimation dye shown in Table 1 was used.
[Preparation example 3]
[Preparation of Y54 dispersion]
A Y54 dispersion was obtained in the same manner as in Preparation Example 1, except that the sublimation dye shown in Table 1 was used.
[Preparation example 4]
[Preparation of Or25 dispersion]
An Or25 dispersion was obtained in the same manner as in Preparation Example 1, except that the sublimation dye shown in Table 1 was used.
[Preparation example 5]
[Preparation of Or60 dispersion]
An Or60 dispersion was obtained in the same manner as in Preparation Example 1, except that the sublimation dye shown in Table 1 was used.
[Preparation example 6]
[Preparation of Bw27 dispersion]
A Bw27 dispersion was obtained in the same manner as in Preparation Example 1, except that the sublimation dye shown in Table 1 was used.
[Preparation Example 7]
[Preparation of R60 dispersion]
An R60 dispersion was obtained in the same manner as in Preparation Example 1, except that the sublimation dye shown in Table 1 was used.

[Preparation example 8]
(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, the mixture was heated to 110°C and reacted for 6 hours. After cooling to 60° C., 100 parts of water was added to the resulting reaction solution, and extraction was performed three times with 50 parts of toluene. After washing the obtained organic layer three times with 100 parts of 1% hydrochloric acid water and once with 100 parts of water, 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 resulting reaction solution, and extraction was performed three times with 50 parts of toluene. After washing the obtained 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 were added to 50 parts of ice water, and the mixture was 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) was added to the obtained reaction solution, and the reaction was carried out at pH 2.0 to pH 2.5, 0 to 10°C for 2 hours, and at pH 3.0 to pH 3.5, 0 to 10°C for 2 hours. carried out. After the reaction was completed, 9.3 parts of the compound represented by formula (14) was obtained by filtering and washing with water.

[Preparation example 9]
(Step 1) Synthesis of a 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 were added to 30 parts of DMF and heated to 100°C. and allowed to react for 6 hours. After cooling to 60° C., 100 parts of water was added to the resulting reaction solution, and extraction was performed three times with 50 parts of toluene. After washing the obtained organic layer three times with 100 parts of water, toluene was distilled off and dried using an evaporator 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 were added to 50 parts of ice water, and the mixture was 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) was added to the obtained reaction solution, and the reaction was carried out at pH 2.0 to pH 2.5, 0 to 10°C for 2 hours, and at pH 3.0 to pH 3.5, 0 to 10°C for 2 hours. carried out. After the reaction was completed, 15.0 parts of the compound represented by formula (10) was obtained by filtering and washing with water.

[Preparation example 10]
(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 were added to 30 parts of DMF and heated to 100°C. and allowed to react for 6 hours. After cooling to 60° C., 100 parts of water was added to the resulting reaction solution, and extraction was performed three times with 50 parts of toluene. After washing the obtained organic layer three times with 100 parts of water, toluene was distilled off and dried using an evaporator 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 were added to 50 parts of ice water, and the mixture was 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) was added to the obtained reaction solution, and the reaction was carried out at pH 2.0 to pH 2.5, 0 to 10°C for 2 hours, and at pH 3.0 to pH 3.5, 0 to 10°C for 2 hours. carried out. After the reaction was completed, 14.0 parts of the compound represented by formula (12) was obtained by filtering and washing with water.

[Preparation example 11]
(Step 1) Synthesis of compound represented by the following 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 below, 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 a compound represented by the following formula (22) 22.6 parts of the compound represented by the formula (21) was added to 90 parts of dehydrated THF and stirred for 30 minutes. To this liquid, 140 parts of borane-THF complex (0.93 mol/l) was added dropwise at 30°C or below over 1 hour, and the mixture was reacted at 30 to 40°C for 1 hour and at 50 to 60°C for 4 hours. 30 parts of water was added dropwise to the reaction solution 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 compound represented by the following formula (23) 21.2 parts of the compound of formula (22), 22.7 parts of potassium carbonate, and 34.7 parts of iodoethane were added to 70 parts of DMF, and the mixture was heated to 100°C. The mixture was heated to a temperature of 100.degree. and reacted for 6 hours. After cooling to 60° C., 250 parts of water was added to the resulting reaction solution, and extraction was performed three times with 200 parts of toluene. After washing the obtained organic layer three times with 200 parts of water, toluene was distilled off and dried using an evaporator to obtain 24.7 parts of a compound represented by the following formula (23).

(Step 4) Synthesis of compound represented by the following 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 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. 12.3 parts of the compound of formula (23) was added to the obtained reaction solution, and the mixture was heated 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. The reaction was carried out. After the reaction was completed, 14.7 parts of the compound represented by formula (24) was obtained by filtering and washing with water.

[Example 1]
[Preparation of colored dispersion 1]
7.22 parts of the compound represented by the above formula (14), which is the compound represented by the above formula (1), and 1.5 parts of the compound represented by the above formula (10), C.I. I. From 6.28 parts of Disperse Blue 360, 4.5 parts of TS-1500, 4.5 parts of SM-57, 0.2 parts of Proxel GXL, 0.4 parts of Surfynol 104PG50, and 75.4 parts of ion exchange water. The mixture was subjected to a dispersion treatment using 0.2 mm diameter glass beads in a sand mill for about 15 hours under cooling. The dye content is 15%. Colored dispersion 1 was obtained by filtration through glass fiber filter paper GC-50 (manufactured by ADVANTEC, filter pore size 0.5 μm).
[Examples 2 to 12, Comparative Examples 1 to 5]
[Preparation of colored dispersions 2 to 17]
Colored dispersions 2 to 17 were prepared in the same manner as in Example 1, except that the type and amount of the compound represented by the above formula (1) and the type and amount of the dispersant were changed as shown in Table 2. Obtained.
The abbreviations in Table 2 below represent the following, respectively.
B360:C. I. Disperse Blue 360
B359:C. I. Disperse Blue 359
Y54:C. I. Disperse Yellow 54
TS-1500: Polyoxyethylene arylphenyl ether dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
SM-57: Polyoxyethylene arylphenyl ether sulfate dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
JC678: Jonkryl 678 (manufactured by BASF Japan Co., Ltd.)

[Preparation of ink]
[Example 13]
43 parts of the colored dispersion 1 obtained in the above Example 1, 6 parts of the B359 dispersion obtained in the above Preparation Example 2, and 6 parts of the Y54 dispersion obtained in the above Preparation Example 3 were mixed, and hereto, 15 parts of glycerin, 10 parts of propylene glycol, 0.1 part of Proxel GXL (manufactured by Lonza), 0.8 part of BYK-348 (manufactured by BYK Chemie Japan), and TEA-80 (manufactured by Junsei Kagaku Co., Ltd.). After adding and stirring 0.1 part of methoxy glycol, 10.0 parts of methoxy glycol, and 14.0 parts of ion-exchanged water, the mixture was filtered through a 5 μm filter to obtain Ink 1 of Example 13. The composition of each dispersion used in the preparation is listed in Table 2 below.
[Examples 14 to 24, Comparative Examples 2 to 8]
Inks 2 to 16 were obtained in the same manner as in Example 13, except that the type and amount of the colored dispersion liquid added were changed as shown in Table 3.

The following evaluation tests were conducted using each of the colored dispersions and inks prepared as described above. The results are shown in Tables 2 and 3 above.

[Intermediate recording medium printed with colored dispersion and sublimation transfer printing using it]
Each of the prepared inks was filled into an inkjet printer (manufactured by EPSON Corporation, trade name PX-504A) and printed at 100% duty or 25% duty using TRANSJET Eco II 8385 (95 g/m ² ) as an intermediate recording medium. Intermediate recording media on which monochrome solid images were printed were obtained. After overlapping the ink-attached surface of each intermediate recording medium obtained with a polyester cloth (Teijin Tropical), it was heated at 200°C for 30 seconds using a tabletop automatic flat press (AF-65TEN, manufactured by Asahi Textile Machinery Co., Ltd.). By heat-treating under the following conditions, dyed products dyed by the sublimation transfer dyeing method were obtained. Each of the obtained dyed products was evaluated as follows.

[Color rendering property 1: Color difference between D65 light source and F2 light source]
Each monochromatic solid dyed product with a duty of 25% was dyed by the sublimation transfer dyeing method using a spectrophotometer “eXact (manufactured by X-rite)” and heat-treated at 200°C for 30 seconds. The hue L*a*b* was measured. The colorimetry was performed using conditions of a viewing angle of 2° and status I, and the values of L ^* a ^* b ^* were obtained for the D65 light source and the F2 light source. The color difference ΔE _D65-F2 was determined from the obtained value of L ^* a ^* b ^* of each light source using the following (Formula 1), and evaluated according to the following evaluation criteria.
The evaluation results are shown in Table 3 above.

△E _D65-F2 = [(L ^* _D65 - L ^* _F2 ) ² + (a ^* _D65 - a ^* _F2 ) ² + (b ^* _D65 - b ^* _F2 ) ² ] ^1/2 (Formula 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 △E _D65-F2 is 5.0 or more.
[Color rendering property 2: Color difference between D65 light source and A light source]
Each monochromatic solid dyed product with a duty of 25% was dyed by the sublimation transfer dyeing method using a spectrophotometer “eXact (manufactured by X-rite)” and heat-treated at 200°C for 30 seconds. The hue L*a*b* was measured. Color measurement was performed using conditions of a viewing angle of 2° and status I, and the values of each L ^* a ^* b ^* were obtained for the D65 light source and the A light source. The color difference ΔE _D65-A was determined from the obtained value of L ^* a ^* b ^* of each light source using the following (Formula 2), and evaluated according to the following evaluation criteria.
The evaluation results are shown in Table 3 above.

△E _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]
100% duty single color solid dyed items dyed by sublimation transfer dyeing method by heat treatment at 200°C x 30 seconds using spectrophotometer “eXact (manufactured by X-rite)” The staining density 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 of each dyed cloth at 400 to 700 nm was measured, and the K/S value was calculated using the Kubelka-Munk formula: K/S=(1-R lambda)2/2R 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 based on the following criteria. The larger the sigma K/S value, the higher the staining density, and therefore the better the quality.
The evaluation results are shown in Table 3 above.
[Evaluation criteria]
A: Sigma K/S value is 470 or more B: Sigma K/S value is 450 or more and less than 470 C: Sigma K/S value is 430 or more and less than 450

[Redispersibility]
25 μL of each of the colored dispersions and inks of the above Examples and Comparative Examples were placed dropwise 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 ion-exchanged water was added dropwise at room temperature, and whether re-dispersion occurred was visually observed and evaluated using the following 4-level criteria.
An ink that can be redispersed without or with less residue is better because it is easier to eliminate clogging after drying. 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 evaluation results are shown in Tables 2 and 3 above.
[Evaluation criteria]
A: Everything was redispersed without any residue.
B: Some residue remains, but most of it has been redispersed.
C: A lot of residue remains, but it has been redispersed to some extent.
D: Not redispersed at all.

[Particle size change]
The median diameter (D50, number average particle diameter) of particles in each colored dispersion that was stored at 60° C. for 5 days was measured using MICRO TRAC UPA EX150 (manufactured by Micro Track Bell Co., Ltd.). Evaluation was made based on the following criteria. In the case of A, B, or C, the storage stability was evaluated as good, and in the case of D, it was evaluated as poor.
The evaluation results are shown in Table 2 above.
[Evaluation criteria]
A: D50 is less than 140 nm B: D50 is 140 nm or more and less than 160 nm C: D50 is 160 nm or more and less than 170 nm D: D50 is 170 nm or more

As is clear from the results in Tables 2 and 3 above, the colored dispersions of Examples 1 to 12 had smaller particle size changes and better storage stability than the colored dispersions of Comparative Examples 1 to 5. In addition, the inks of Examples 13 to 24 using the colored dispersions of Examples 1 to 12 had smaller particle size changes and had better storage stability than Comparative Examples 6 to 9, which used the colored dispersions of Comparative Examples 1 to 5. It can be seen that the color is good, the color rendering property and the color development are also high, and a high quality black color is exhibited. In addition, the colored dispersion containing the dye represented by formula (1) according to the present invention has excellent redispersibility and injection properties, has high transfer efficiency, and can provide dyed products with high dye density and excellent tone. This shows that the ink is extremely useful as various recording inks, especially inkjet textile inks.

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

Claims (9)

(A) a compound represented by the following formula (1), (B) C.I. I. DisperseBlue 360, (C) a dispersant, and when the total content of (A) and (B) is 100 % by mass, the content of (B) is 14.7 % by mass or more and 85.3 % by mass or less. (C) A colored dispersion containing at least one selected from the group consisting of 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 represent a C1 to C4 alkyl group which may be substituted with a C1 to C4 alkoxy group or a phenyl group. (R ⁴ represents a halogen atom. R ² and R ³ may be linked to each other to form a ring.) The colored dispersion according to claim 1, wherein R ⁴ in the above formula (1) 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 to C4 alkyl group which may be substituted with a C1 to C4 alkoxy group, and R ⁴ is a chlorine atom. The colored dispersion described in . In the ultraviolet-visible spectral absorption of a solution dissolved in acetone, one type of yellow dye has a maximum absorption wavelength in the wavelength range of 620 nm or more and less than 700 nm, and in the ultraviolet-visible spectral absorption of a solution dissolved in acetone. The colored dispersion according to any one of claims 1 to 3, further comprising one kind of blue dye having a maximum absorption wavelength in a wavelength range of 550 nm or more and less than 620 nm. The colored dispersion according to any one of claims 1 to 4, further comprising a water-soluble organic solvent. A recording medium to which the colored dispersion according to any one of claims 1 to 5 is attached. The recording medium according to claim 6, wherein the recording medium is a fiber. The recording medium according to claim 7, wherein the fibers are hydrophobic fibers. The recording medium according to claim 8, wherein the hydrophobic fiber is polyester or a blended fiber containing polyester.