JP7682109B2 - Colored dispersion, recording medium, and method for printing hydrophobic fibers - Google Patents

Description

The present invention relates to a colored dispersion, a recording medium to which the colored dispersion is adhered, and a method for printing hydrophobic fibers using the colored dispersion.

In recent years, a recording method for plate-less printing using inkjet printing has been proposed, and inkjet printing (inkjet printing) is also being used for printing on textiles, including cloth. Inkjet printing has various advantages over conventional printing methods such as screen printing, including no plate-making required, resource saving, energy saving, and ease of high-resolution expression.

Here, hydrophobic fibers, such as polyester fibers, are generally dyed with water-insoluble colorants. For this reason, the aqueous ink used to print hydrophobic fibers by inkjet printing generally requires a dispersion ink with good performance, such as dispersion stability, in which a water-insoluble colorant is dispersed in water.

Inkjet printing methods for hydrophobic fibers can be broadly divided into direct printing and sublimation transfer. Direct printing is a printing method in which ink is applied (printed) directly onto hydrophobic fibers, and then the dye in the ink is caused to adhere to the hydrophobic fibers by heat treatment such as high-temperature steaming. On the other hand, sublimation transfer is a printing method in which ink is applied (printed) onto an intermediate recording medium (such as dedicated transfer paper), the ink-applied surface of the intermediate recording medium is superimposed on the hydrophobic fibers, and then the dye is transferred from the intermediate recording medium to the hydrophobic fibers by heat.

The sublimation transfer method is mainly used in the printing of flags and other items, and the ink contains an easily sublimable dye that is highly suitable for transfer to hydrophobic fibers through heat treatment. The process involves two steps: (1) printing: applying the dye ink to an intermediate recording medium using an inkjet printer, and (2) transfer: transferring and dyeing the dye from the intermediate recording medium to the fibers through heat treatment. Since commercially available transfer paper can be widely used, no pretreatment of the fibers is required, and the washing step is omitted.

As ink for the sublimation transfer method, aqueous inks in which water-insoluble dyes are dispersed in water are generally used. For example, Patent Document 1 describes the preparation of aqueous inks by adding a water-soluble organic solvent as a moisturizing agent (anti-drying agent), a surfactant as a surface tension adjuster, and other additives (pH adjusters, antiseptics, antifungals, defoamers, etc.) to a dye dispersion liquid in which a water-insoluble dye selected from disperse dyes and oil-soluble dyes is dispersed in water with a dispersant, and optimizing physical properties (physical properties) such as particle size, viscosity, surface tension, and pH.

International Publication No. 2005/121263 Patent No. 6191234

However, when the inventors studied conventional aqueous inks in which a water-insoluble dye was dispersed in water, they found that even if the dispersion stability of the dye dispersion was relatively good, when a surfactant or other component was added to the dye dispersion to prepare an aqueous ink, the particles in the aqueous ink aggregated, resulting in a decrease in dispersion stability.

The present invention aims to provide a colored dispersion liquid that has excellent dispersion stability and suppresses particle aggregation during storage, a recording medium to which the colored dispersion liquid is adhered, and a method for printing hydrophobic fibers using the colored dispersion liquid.

（式（１ａ）中、Ｒ^１ａは、水素原子、置換基を有していてもよい炭素数１～４のアルキル基、又は置換基を有していてもよいフェニル基を示す。Ｒ^２ａ、Ｒ^３ａはそれぞれ独立に、水素原子又はシアノ基を示す。Ｘ^ａは、水素原子、ヒドロキシ基、又は－ＮＨＲ^４ａで表される基を示す。Ｒ^４ａは、水素原子、又は置換基を有していてもよいフェニル基を示す。）

（式（１ｂ）中、Ｒ^１ｂ、Ｒ^２ｂはそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１～２０のアルキル基を示す。）

（式（１ｃ）中、Ｒ^１ｃ～Ｒ^１０ｃはそれぞれ独立に、水素原子、ハロゲン原子、置換基を有していてもよい炭素数１～４のアルキル基、置換基を有してもいてよいフェニル基、又はヒドロキシ基を示す。）

（式（２ａ）中、Ｒ^５ａ、Ｒ^６ａはそれぞれ独立に、置換基を有していてもよい炭素数１～６のアルキル基を示す。Ｒ^７ａ、Ｒ^８ａはそれぞれ独立に、水素原子又はハロゲン原子を示す。）

（式（２ｂ）中、Ａ^ｂは、炭素原子又は窒素原子を示す。ｎは０～１の値を表す。Ｒ^３ｂ、Ｒ^４ｂはそれぞれ独立に、置換基を有していてもよい脂肪族基を示す。Ｒ^３ｂ、Ｒ^４ｂは、互いに結合して置換基を有していてもよい単環又は縮環を形成していてもよい。Ｒ^５ｂは、置換基を有していてもよい脂肪族基を示す。Ｒ^３ｂ、Ｒ^４ｂ、Ｒ^５ｂは、互いに結合して置換基を有していてもよい縮環を形成していてもよい。Ｒ^６ｂ、Ｒ^７ｂはそれぞれ独立に、水素原子、ヒドロキシ基、又は臭素原子を示す。Ｒ^８ｂ、Ｒ^９ｂはそれぞれ独立に、置換基を有していてもよい脂肪族基を示す。Ｒ^８ｂ、Ｒ^９ｂは、互いに結合して置換基を有していてもよい単環又は縮環を形成していてもよい。但し、ｎ、Ａ^ｂ、Ｒ^３ｂ～Ｒ^９ｂの組み合わせとして、前記式（１ｂ）で表される化合物となる組み合わせは除く。）

（式（２ｃ－１）中、Ｒ^１１ｃ～Ｒ^１６ｃはそれぞれ独立に、水素原子、置換基を有していてもよい炭素数１～６のアルキル基、ハロゲン原子、－ＮＨＲ^１７ｃで表される基、又は－ＯＲ^１８ｃで表される基を示す。Ｒ^１７ｃ、Ｒ^１８ｃはそれぞれ独立に、水素原子、又は置換基を有していてもよい炭素数１～６のアルキル基を示す。）

（式（２ｃ－２）中、Ｒ^１９ｃ～Ｒ^２３ｃはそれぞれ独立に、水素原子、置換基を有していてもよい炭素数１～６のアルキル基、ハロゲン原子、又は－ＯＲ^２４ｃで表される基を示す。Ｒ^２４ｃは、水素原子、又は置換基を有していてもよい炭素数１～６のアルキル基を示す。）

（式（２ｄ－１）中、Ｒ^１ｄ、Ｒ^２ｄはそれぞれ独立に、水素原子、置換基を有していてもよい炭素数１～２のアルキル基、又はシアノ基を示す。但し、Ｒ^１ｄ、Ｒ^２ｄが同時に水素原子を示す場合を除く。Ｒ^３ｄ、Ｒ^４ｄはそれぞれ独立に、水素原子、置換基を有していてもよい炭素数１～２のアルキル基、又はハロゲン原子を示す。）

（式（２ｄ－２）中、Ｒ^５ｄ、Ｒ^６ｄはそれぞれ独立に、水素原子、又は置換基を有していてもよい炭素数１～２のアルキル基を示す。）

（式（２ｄ－３）中、Ｒ^７ｄは、メトキシ基又は水素原子を示す。Ｒ^８ｄは、ハロゲン原子、又は－ＮＨＣＯＣＨ_３で表される基を示す。Ｒ^９ｄ、Ｒ^１０ｄは、置換基を有していてもよい炭素数１～２のアルキル基、又は－Ｃ_２Ｈ_４ＯＣＯＣ_２Ｈ_５で表される基を示す。） Specific means for solving the above problems include the following embodiments.
1)
(A) a dye represented by any one of the following formulas (1a) to (1c) or C.I. Disperse Blue 360; (B) a dye derivative represented by any one of the following formulas (2a), (2b), (2c-1), (2c-2), (2d-1) to (2d-3); and water;
The combination of the dye (A) and the dye derivative (B) is any one of the following combinations (a) to (d):
(a) a combination of a compound represented by the following formula (1a) and a compound represented by the following formula (2a):
(b) a combination of a compound represented by the following formula (1b) and a compound represented by the following formula (2b):
(c) a combination of a compound represented by the following formula (1c) with at least one compound selected from a compound represented by the following formula (2c-1) and a compound represented by the following formula (2c-2):
(d) A combination of C.I. Disperse Blue 360 and at least one compound selected from the group consisting of a compound represented by the following formula (2d-1), a compound represented by the following formula (2d-2), and a compound represented by the following formula (2d-3):
Either
The color dispersion liquid has a content of the dye derivative (B) of less than 10 parts by mass when the total content of the dye (A) and the dye derivative (B) is taken as 100 parts by mass.

(In formula (1a), R ^1a represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. R ^2a and R ^3a each independently represent a hydrogen atom or a cyano group. ^Xa represents a hydrogen atom, a hydroxy group, or a group represented by -NHR ^4a . R ^4a represents a hydrogen atom or a phenyl group which may have a substituent.)

(In formula (1b), R ^1b and R ^2b each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent.)

(In formula (1c), R ^1c to R ^10c each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a hydroxy group.)

(In formula (2a), R ^5a and R ^6a each independently represent an alkyl group having 1 to 6 carbon atoms which may have a substituent. R ^7a and R ^8a each independently represent a hydrogen atom or a halogen atom.)

(In formula (2b), A ^b represents a carbon atom or a nitrogen atom. n represents a value of 0 to 1. R ^3b and R ^4b each independently represent an aliphatic group which may have a substituent. R ^3b and R ^4b may be bonded to each other to form a monocyclic or condensed ring which may have a substituent. R ^5b represents an aliphatic group which may have a substituent. R ^3b , R ^4b and R ^5b may be bonded to each other to form a condensed ring which may have a substituent. R ^6b and R ^7b each independently represent a hydrogen atom, a hydroxyl group or a bromine atom. R ^8b and R ^9b each independently represent an aliphatic group which may have a substituent. R ^8b and R ^9b may be bonded to each other to form a monocyclic or condensed ring which may have a substituent. However, combinations of n, A ^b and R ^3b to R ^9b that result in a compound represented by formula (1b) are excluded.)

(In formula (2c-1), R ^11c to R ^16c each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, a halogen atom, a group represented by -NHR ^17c , or a group represented by -OR ^18c . R ^17c and R ^18c each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.)

(In formula (2c-2), R ^19c to R ^23c each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, a halogen atom, or a group represented by —OR ^24c . R ^24c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.)

(In formula (2d-1), R ^1d and R ^2d each independently represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms which may have a substituent, or a cyano group, except for the case where R ^1d and R ^2d simultaneously represent a hydrogen atom. R ^3d and R ^4d each independently represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms which may have a substituent, or a halogen atom.)

(In formula (2d-2), R ^5d and R ^6d each independently represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms which may have a substituent.)

(In formula (2d-3), R ^7d represents a methoxy group or a hydrogen atom. R ^8d represents a halogen atom or a group represented by -NHCOCH _3. ^{R 9d} and R ^10d each represent an alkyl group having 1 to 2 carbon atoms which may have a substituent, or a group represented by -C ₂ H ₄ OCOC ₂ H _5. )

2)
The color dispersion liquid according to 1), wherein the content of the dye derivative (B) is 0.1 to 5 parts by mass when the total content of the dye (A) and the dye derivative (B) is 100 parts by mass.

3)
The color dispersion liquid according to 1), wherein the content of the specific compound (B) is 0.5 to 5 parts by mass when the total content of the dye (A) and the dye derivative (B) is 100 parts by mass.

4)
The colored dispersion according to any one of items 1) to 3), wherein the compound represented by formula (1a) is C.I. Disperse Blue 359.

5)
The colored dispersion according to any one of items 1) to 3), wherein the compound represented by formula (1b) is C.I. Disperse Yellow 54.

6)
The colored dispersion according to any one of items 1) to 3), wherein the compound represented by formula (1c) is C.I. Solvent Orange 60.

7)
The colored dispersion according to any one of 1) to 6), further comprising a dispersant.

8)
8) The colored dispersion according to 7), wherein the dispersant contains a formalin condensate of an aromatic sulfonic acid or a salt thereof.

9)
8) The colored dispersion according to 8), wherein the formalin condensate of an aromatic sulfonic acid or a salt thereof is a formalin condensate of sodium naphthalenesulfonate or a salt thereof.

10)
9) The colored dispersion according to 8), wherein the formalin condensate of an aromatic sulfonic acid or a salt thereof is a formalin condensate of a creosote oil sulfonic acid or a salt thereof.

11)
10) The color dispersion according to any one of claims 7) to 10), wherein the dispersant comprises a phytosterol compound.

12)
7) The color dispersion liquid according to 7), wherein the dispersant comprises at least one selected from polyoxyethylene aryl phenyl ether-based dispersants and polyoxyethylene aryl phenyl ether sulfate-based dispersants.

13)
A recording medium having the colored dispersion liquid according to any one of 1) to 12) adhered thereto.

14)
14) The recording medium according to 13), which is made of hydrophobic fibers.

15)
A printing step in which droplets of the color dispersion according to any one of 1) to 12) are deposited on an intermediate recording medium to obtain a recorded image;
a transfer step of contacting a hydrophobic fiber with a surface of the intermediate recording medium to which the color dispersion liquid has been applied and heat-treating the hydrophobic fiber to transfer the recorded image to the hydrophobic fiber;
A method for printing hydrophobic fibers comprising the steps of:

According to the present invention, it is possible to provide a colored dispersion liquid that has excellent dispersion stability and suppresses particle aggregation during storage, a recording medium to which the colored dispersion liquid is adhered, and a printing method for hydrophobic fibers using the colored dispersion liquid.

<Colored dispersion>
The color dispersion according to this embodiment contains (A) a dye which is a compound represented by any one of the above formulas (1a) to (1c) or C.I. Disperse Blue 360, (B) a dye derivative which is a compound represented by any one of the above formulas (2a), (2b), (2c-1), (2c-2), (2d-1) to (2d-3), and water. "C.I." is an abbreviation for Color Index.

However, the combination of the dye (A) and the dye derivative (B) in the colored dispersion liquid according to this embodiment is any one of the following combinations (a) to (d).
(a) A combination of a compound represented by the above formula (1a) and a compound represented by the above formula (2a).
(b) A combination of a compound represented by the above formula (1b) and a compound represented by the above formula (2b).
(c) A combination of a compound represented by the above formula (1c) with at least one compound selected from the compound represented by the above formula (2c-1) and the compound represented by the above formula (2c-2).
(d) A combination of C.I. Disperse Blue 360 and at least one compound selected from the compounds represented by the above formula (2d-1), the compounds represented by the above formula (2d-2), and the compounds represented by the above formula (2d-3).

In addition, in the colored dispersion liquid according to this embodiment, the content of the (B) dye derivative is less than 10 parts by mass when the total content of the (A) dye and the (B) dye derivative is 100 parts by mass. By setting the content of the (B) dye derivative at the above ratio, it tends to be possible to stably maintain the dispersed state of the particles in the colored dispersion liquid. When the total content of the (A) dye and the (B) dye derivative is 100 parts by mass, the content of the (B) dye derivative is preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 5 parts by mass.

[Compound represented by formula (1a)]
In the above formula (1a), R ^1a represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. R ^2a and R ^3a each independently represent a hydrogen atom or a cyano group. ^Xa represents a hydrogen atom, a hydroxyl group, or a group represented by -NHR ^4a . R ^4a represents a hydrogen atom or a phenyl group which may have a substituent.

Examples of alkyl groups having 1 to 4 carbon atoms include linear alkyl groups such as methyl, ethyl, n-propyl, and n-butyl groups; branched alkyl groups such as isopropyl, sec-butyl, and tert-butyl groups; and the like.

Examples of substituents that an alkyl group having 1 to 4 carbon atoms may have include a hydroxy group, a carboxy group, a sulfo group, a phosphate group, a silanol group, a halogen atom, a cyano group, a nitro group, an amino group, an alkoxy group, an aryloxy group, a silyloxy group, a carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an alkylcarboxy group, an arylcarboxy group, a heterocyclic group, and an aromatic ring group. These substituents may further have any optional substituent.

Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

Examples of amino groups include amino groups, methylamino groups, ethylamino groups, n-butylamino groups, phenylamino groups, dimethylamino groups, diethylamino groups, di-n-butylamino groups, diphenylamino groups, dinaphthylamino groups, ethylmethylamino groups, and methylphenylamino groups.

Examples of alkoxy groups include methoxy groups, ethoxy groups, n-butoxy groups, and tert-butoxy groups.

Examples of aryloxy groups include phenoxy and naphthoxy groups.

Examples of silyloxy groups include trimethylsilyloxy groups and tert-butyldimethylsilyloxy groups.

Examples of alkylcarbonyl groups include acetyl groups, ethylcarbonyl groups, and n-butylcarbonyl groups.

Examples of arylcarbonyl groups include phenylcarbonyl groups, naphthylcarbonyl groups, and fluorenocarbonyl groups.

Examples of alkoxycarbonyl groups include methoxycarbonyl groups and ethoxycarbonyl groups.

Examples of alkyl carboxy groups include methyl carboxy groups, ethyl carboxy groups, and n-butyl carboxy groups.

Examples of aryl carboxy groups include phenyl carboxy groups.

Examples of heterocyclic groups include thiophene groups, furan groups, pyrrole groups, thiazole groups, and benzothiazole groups.

Examples of aromatic ring groups include phenyl groups, naphthyl groups, and fluorenyl groups.

Examples of the substituents that the phenyl group may have include alkyl groups and the same as the substituents in the above "alkyl groups having 1 to 4 carbon atoms which may have a substituent." These substituents may further have any optional substituents.

When the phenyl group has an alkyl group as a substituent, examples of the alkyl group include linear alkyl groups such as methyl groups, ethyl groups, n-propyl groups, n-butyl groups, n-pentyl groups, n-hexyl groups, and n-octyl groups; branched alkyl groups such as isopropyl groups, sec-butyl groups, tert-butyl groups, and neopentyl groups; and cyclic alkyl groups such as cyclopentyl groups and cyclohexyl groups; and other alkyl groups having 1 to 8 carbon atoms.

R ^1a in the above formula (1a) is preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, and more preferably an ethyl group or a phenyl group substituted with a methyl group at the p-position.

It is preferable that R ^2a and R ^3a in the above formula (1a) are both hydrogen atoms, or one of them is a cyano group and the other is a hydrogen atom.

^Xa in the above formula (1a) is preferably a hydroxy group or a group represented by --NHR ^4a , and more preferably a hydroxy group or a group in which R ^4a of --NHR ^4a is a hydrogen atom or a methyl group.

Among the compounds represented by the above formula (1a), preferred examples include C.I. Disperse Blue 72, 359; C.I. Solvent Blue 63; and the like, with C.I. Disperse Blue 359 being preferred.

[Compound represented by formula (1b)]
In the above formula (1b), R ^1b and R ^2b each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms.

Examples of alkyl groups having 1 to 20 carbon atoms include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-octyl groups; branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neopentyl groups; and the like.

Examples of the substituents that an alkyl group having 1 to 20 carbon atoms may have include the same groups as the substituents in the above "alkyl group having 1 to 4 carbon atoms which may have a substituent."

In the above formula (1b), R ^1b and R ^2b are both preferably a hydrogen atom.

Among the compounds represented by the above formula (1b), a preferred example is C.I. Disperse Yellow 54.

[Compound represented by formula (1c)]
In the above formula (1c), R ^1c to R ^10c each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, or a hydroxy group.

Examples of the halogen atom, the alkyl group having 1 to 4 carbon atoms which may have a substituent, and the phenyl group which may have a substituent include the same groups as those described above.

In the above formula (1c), it is preferable that R ^1c to R ^10c are each independently a hydrogen atom or a halogen atom.

Among the compounds represented by the above formula (1c), preferred ones include, for example, C.I. Solvent Orange 60; C.I. Solvent Red 135, 176; and the like, with C.I. Solvent Orange 60 being preferred.

[Compound represented by formula (2a)]
In the above formula (2a), R ^5a and R ^6a each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ^7a and R ^8a each independently represent a hydrogen atom or a halogen atom.

Examples of alkyl groups having 1 to 6 carbon atoms include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl groups; branched alkyl groups such as isopropyl, sec-butyl, and tert-butyl groups; and cyclic alkyl groups such as cyclopentyl and cyclohexyl groups.

Examples of the substituents that an alkyl group having 1 to 6 carbon atoms may have include the same groups as the substituents in the above "alkyl group having 1 to 4 carbon atoms which may have a substituent."

The halogen atoms may be the same as above.

It is preferable that R ^5a and R ^6a in the above formula (2a) each independently represent an alkyl group having 1 to 6 carbon atoms, more preferably each independently represent a methyl group, an ethyl group, an n-butyl group, or an isopropyl group, and further preferably both represent a methyl group, an ethyl group, an n-butyl group, or an isopropyl group, or one of them is a methyl group and the other is an isopropyl group.

In the above formula (2a), R ^7a and R ^8a are preferably each independently a hydrogen atom or a chlorine atom, and it is more preferable that both are hydrogen atoms or both are chlorine atoms.

Among the compounds represented by the above formula (2a), preferred examples include C.I. Solvent Blue 35, 36, 78, 102, 105, 112, etc.

[Compound represented by formula (2b)]
In the above formula (2b), A ^b represents a carbon atom or a nitrogen atom. n represents a value of 0 to 1. R ^3b and R ^4b each independently represent an aliphatic group which may have a substituent. R ^3b and R ^4b may be bonded to each other to form a monocyclic or condensed ring which may have a substituent. R ^5b represents an aliphatic group which may have a substituent. R ^3b , R ^4b and R ^5b may be bonded to each other to form a condensed ring which may have a substituent. R ^6b and R ^7b each independently represent a hydrogen atom, a hydroxyl group, or a bromine atom. R ^8b and R ^9b each independently represent an aliphatic group which may have a substituent. R ^8b and R ^9b may be bonded to each other to form a monocyclic or condensed ring which may have a substituent. However, as a combination of n, A ^b , and R ^3b to R ^9b , a combination that results in a compound represented by the above formula (1b) is excluded.

Examples of aliphatic groups include the above-mentioned "alkyl groups having 1 to 20 carbon atoms, which may have a substituent," as well as alkenyl groups, alkynyl groups, etc.

Examples of the substituents that the aliphatic group may have include the same as the substituents in the above-mentioned "alkyl group having 1 to 4 carbon atoms which may have a substituent."

Examples of monocyclic rings which may have a substituent include a benzene ring, a pyridine ring, a cyclohexane ring, a quinone ring, etc.

Examples of fused rings which may have a substituent include a naphthalene ring, an anthracene ring, a benzothiazole ring, and a naphthothiazole ring. When an isomer is present in the fused ring, any isomer may be present, or multiple isomers may be present.

^Ab in the above formula (2b) is preferably a nitrogen atom.

In the above formula (2b), ^R3b and ^R4b are preferably bonded to each other to form a monocyclic or condensed ring which may have a substituent, and more preferably to form a benzene ring which may have a substituent. The substituent is preferably a halogen atom, an aromatic ring group, or an alkoxycarbonyl group.

When n is 1, R ^5b in the above formula (2b) is preferably an aliphatic group, and it is more preferable that R ^3b , R ^4b and R ^5b are bonded to each other to form a condensed ring which may have a substituent.

It is preferable that R ^6b and R ^7b in the above formula (2b) are both hydrogen atoms, one of them is a hydroxy group and the other is a hydrogen atom, or one of them is a hydroxy group and the other is a bromine atom.

In the above formula (2b), R ^8b and R ^9b are preferably bonded to each other to form a monocyclic or condensed ring which may have a substituent, and more preferably to form a benzene ring which may have a substituent. Preferred examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a halogen atom, an aromatic ring group, and an alkoxycarbonyl group.

Preferred combinations of n, A ^b , and R ^3b to R ^9b in the above formula (2b) include, for example, a combination in which n is 0, A ^b is a nitrogen atom, R ^3b and R ^4b are bonded to each other to form a benzene ring which may have a substituent, R ^6b is a hydroxy group, R ^8b and R ^9b are bonded to each other to form a benzene ring which may have a substituent, and one to three of the substituents on the benzene ring formed by R ^7b , R ^3b and R ^4b bonded to each other, and the substituents on the benzene ring formed by R ^8b and R ^9b bonded to each other are each independently an atom or group selected from the group consisting of a bromine atom, a phenyl group, and an alkoxycarbonyl group.

Among the compounds represented by the above formula (2b), preferred examples include C.I. Disperse Yellow 64, 134, 143, 149, and 160. C.I. Disperse Yellow 134 is represented by the following formula:

[Compound represented by formula (2c-1)]
In the above formula (2c-1), R ^11c to R ^16c each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, a halogen atom, a group represented by -NHR ^17c , or a group represented by -OR ^18c . ^{R 17c} and R ^18c each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms and the halogen atom which may have a substituent include the same groups as those mentioned above.

In the above formula (2c-1), R ^11c to R ^16c are preferably each independently a hydrogen atom, a group represented by -NHR ^17c , or a group represented by -OR ^18c . In this case, R ^17c is preferably a methyl group or a hydroxyethyl group, and R ^18c is preferably a methyl group.

Among the compounds represented by the above formula (2c-1), preferred examples include C.I. Solvent Red 179, 180; C.I. Solvent Orange 79; C.I. Solvent Yellow 119; and the like.

[Compound represented by formula (2c-2)]
In the above formula (2c-2), R ^19c to R ^23c each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, a halogen atom, or a group represented by -OR ^24c , where R ^24c represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms and the halogen atom which may have a substituent include the same groups as those mentioned above.

In the above formula (2c-2), R ^19c to R ^23c are preferably all hydrogen atoms.

Among the compounds represented by the above formula (2c-2), preferred examples include C.I. Disperse Orange 118, etc.

[Compound represented by formula (2d-1)]
In the above formula (2d-1), R ^1d and R ^2d each independently represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms which may have a substituent, or a cyano group, except when R ^1d and R ^2d simultaneously represent a hydrogen atom. ^{R 3d} and R ^4d each independently represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms which may have a substituent, or a halogen atom.

Examples of alkyl groups having 1 to 2 carbon atoms include methyl and ethyl groups. Examples of the substituents that may be carried by the alkyl groups having 1 to 2 carbon atoms include the same groups as the substituents in the above "alkyl groups having 1 to 4 carbon atoms which may be substituted."

The halogen atoms may be the same as above.

Among the compounds represented by the above formula (2d-1), preferred ones include, for example, the compounds represented by the following formulas (2d-1-1) to (2d-1-3).

[Compound represented by formula (2d-2)]
In the above formula (2d-2), R ^5d and R ^6d each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 2 carbon atoms. Examples of the optionally substituted alkyl group having 1 to 2 carbon atoms include the same groups as those mentioned above.

Among the compounds represented by the above formula (2d-2), preferred ones include, for example, the compounds represented by the following formulas (2d-2-1) to (2d-2-4).

[Compound represented by formula (2d-3)]
In the above formula (2d-3), R ^7d represents a methoxy group or a hydrogen atom. R ^8d represents a halogen atom, or a group represented by -NHCOCH _3. ^{R 9d} and R ^10d represent an alkyl group having 1 to 2 carbon atoms which may have a substituent, or a group represented by -C ₂ H ₄ OCOC ₂ H _5. Examples of the alkyl group having 1 to 2 carbon atoms which may have a substituent include the same groups as above.

Among the compounds represented by the above formula (2d-3), preferred ones include, for example, the compounds represented by the following formulas (2d-3-1) to (2d-3-4).

The total content of (A) dye and (B) dye derivative is preferably 10 to 25% by mass, and more preferably 14 to 17% by mass, based on the total amount of the colored dispersion.

[Other colorants]
The colored dispersion according to the present embodiment may further contain other colorants in addition to the above-mentioned (A) dye and (B) dye derivative. However, it is preferable that the content of the (A) dye is the highest among the (A) dye, (B) dye derivative, and other colorants in the colored dispersion.

Other colorants include, for example, pigments, disperse dyes, oil-soluble dyes, acid dyes, reactive dyes, direct dyes, etc., with disperse dyes and oil-soluble dyes being preferred, and disperse dyes being more preferred.

For example, when the (A) pigment and the (B) pigment derivative are combined as described above in (a) and (d), examples of the disperse dye include C.I. Disperse Blue dyes other than the (A) pigment and the (B) pigment derivative. When the (A) pigment and the (B) pigment derivative are combined as described above in (b), examples of the disperse dye include C.I. Disperse Yellow dyes other than the (A) pigment and the (B) pigment derivative. When the (A) pigment and the (B) pigment derivative are combined as described above in (c), examples of the disperse dye include C.I. Disperse Orange dyes other than the (A) pigment and the (B) pigment derivative.

The content of other colorants is preferably 10% by mass or less, and more preferably 6% by mass or less, relative to the total amount of the color dispersion.

[water]
The water used is preferably ion-exchanged water, distilled water, or other water containing few impurities. Sterilized water may also be used.

The content of water in the colored dispersion is appropriately selected depending on the application. The content of water in the colored dispersion is usually 200 to 8,500 parts by mass per 100 parts by mass of the total of (A) the dye, (B) the dye derivative, and any other colorants that may be optionally contained.

[Dispersant]
The color dispersion according to this embodiment preferably further contains a dispersant.

The dispersant preferably contains, for example, a formalin condensate of aromatic sulfonic acid or a salt thereof. The formalin condensate of aromatic sulfonic acid or a salt thereof is an anionic surfactant obtained by a condensation reaction between aromatic sulfonic acid and formalin.

Examples of formalin condensates of aromatic sulfonic acids or their salts include formalin condensates of creosote oil sulfonic acid, cresol sulfonic acid, phenol sulfonic acid, naphthalene sulfonic acid, β-naphthol sulfonic acid, β-naphthalene sulfonic acid and β-naphthol sulfonic acid, benzene sulfonic acid, cresol sulfonic acid, 2-naphthol-6-sulfonic acid, lignin sulfonic acid, etc., or their salts (sodium salt, potassium salt, lithium salt, etc.). Among these, formalin condensates of creosote oil sulfonic acid, naphthalene sulfonic acid, lignin sulfonic acid, and methylnaphthalene sulfonic acid or their salts are preferred. Examples of naphthalene sulfonic acids include α-naphthalene sulfonic acid and β-naphthalene sulfonic acid, and β-naphthalene sulfonic acid is preferred.

Formalin condensates of aromatic sulfonic acids or their salts can also be obtained as commercial products. For example, formalin condensates of β-naphthalenesulfonic acid or their salts include Demol N (manufactured by Kao Corporation). Formalin condensates of creosote oil sulfonic acid or their salts include Demol C (manufactured by Kao Corporation) and Labelin W series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). Formalin condensates of special aromatic sulfonic acids or their salts include Demol SN-B (manufactured by Kao Corporation). Formalin condensates of methylnaphthalenesulfonic acid or their salts include Labelin AN series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). Of these, Demol N, Labelin AN series, and Labelin W series are preferred, Demol N and Labelin W series are more preferred, and Labelin W series is even more preferred. Examples of lignin sulfonic acid include Vanilex N, Vanilex RN, Vanilex G, and Pearlex DP (all manufactured by Nippon Paper Industries Co., Ltd.). Among these, Vanilex RN, Vanilex N, and Vanilex G are preferred.

Dispersants other than the formalin condensate of aromatic sulfonic acid or its salt include known dispersants, surfactants, resin dispersants, etc. In addition, the terms dispersant and surfactant may refer to the same substance. Types of dispersants include anionic dispersants, nonionic dispersants, cationic dispersants, amphoteric dispersants, etc. Among these, at least one type of dispersant selected from anionic dispersants and nonionic dispersants is preferred.

Examples of anionic dispersants other than formalin condensates of aromatic sulfonic acids or their salts include polymeric sulfonic acids, lignin sulfonic acids, formalin condensates of lignin sulfonic acids or their salts.

Examples of nonionic dispersants include alkylene oxide adducts of phytosterols, alkylene oxide adducts of cholestanols, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, oxyethyleneoxypropylene block polymers, and substituted derivatives thereof. Among these, alkylene oxide adducts of phytosterols (also called phytosterol compounds) and alkylene oxide adducts of cholestanols (also called cholestanol compounds) are preferred, with phytosterol compounds being more preferred.

As the alkylene oxide adduct of phytosterols, C2-C4 alkylene oxide adducts of phytosterols are preferred, and ethylene oxide adducts are more preferred. In this specification, "phytosterols" is used to mean both "phytosterol" and "hydrogenated phytosterol". For example, ethylene oxide adducts of phytosterols include ethylene oxide adducts of phytosterol and ethylene oxide adducts of hydrogenated phytosterol.

As the alkylene oxide adduct of cholestanol, a C2-C4 alkylene oxide adduct of cholestanol is preferred, and an ethylene oxide adduct is more preferred. In this specification, "cholestanol" is used to mean both "cholestanol" and "hydrogenated cholestanol". For example, examples of the ethylene oxide adduct of cholestanol include an ethylene oxide adduct of cholestanol and an ethylene oxide adduct of hydrogenated cholestanol.

The amount of alkylene oxide (preferably C2-C4 alkylene oxide, more preferably ethylene oxide) added per mole of phytosterols or cholestanols is preferably about 10 to 50 moles, and the HLB is preferably about 13 to 20.

Commercially available alkylene oxide adducts of phytosterols include, for example, NIKKOL BPS-20 and NIKKOL BPS-30 (both manufactured by Nikko Chemicals Co., Ltd., ethylene oxide adducts of phytosterols), and NIKKOL BPSH-25 (same manufacturer, ethylene oxide adduct of hydrogenated phytosterols). Commercially available alkylene oxide adducts of cholestanols include, for example, NIKKOL DHC-30 (manufactured by Nikko Chemicals Co., Ltd., ethylene oxide adduct of cholestanol).

Examples of resin dispersants include styrene-(meth)acrylic copolymers. Styrene-(meth)acrylic copolymers are copolymers of styrene-based monomers and (meth)acrylic monomers. Specific examples of copolymers include (α-methyl)styrene-acrylic acid copolymers, (α-methyl)styrene-acrylic acid-acrylic acid ester copolymers, (α-methyl)styrene-methacrylic acid copolymers, (α-methyl)styrene-methacrylic acid-acrylic acid ester copolymers, (α-methyl)styrene-acrylic acid ester-(anhydride) maleic acid copolymers, acrylic acid ester-styrene sulfonic acid copolymers, and (α-methyl)styrene-methacrylic acid sulfonic acid copolymers. In this specification, "(meth)acrylic" is used to mean "acrylic" and "methacrylic". Furthermore, "(α-methyl)styrene" is used to mean "α-methylstyrene" and "styrene".

The mass average molecular weight of the styrene-(meth)acrylic copolymer is, for example, preferably 1,000 to 20,000, more preferably 2,000 to 19,000, and even more preferably 5,000 to 17,000. The mass average molecular weight of the styrene-(meth)acrylic copolymer can be measured by GPC (gel permeation chromatography).

The acid value of the styrene-(meth)acrylic copolymer is, for example, preferably 50 to 250 mgKOH/g, more preferably 100 to 250 mgKOH/g, and even more preferably 150 to 250 mgKOH/g. By making the acid value 50 mgKOH/g or more, the solubility in water is improved and the dispersion stabilizing power tends to be improved. Furthermore, by making the acid value 250 mgKOH/g or less, bleeding of the printed image due to increased affinity with the aqueous medium tends to be suppressed. The acid value of the resin represents the number of mg of KOH required to neutralize 1 g of resin, and can be measured according to JIS-K3054.

The glass transition temperature of the styrene-(meth)acrylic copolymer is, for example, preferably 45 to 135°C, more preferably 55 to 120°C, and even more preferably 60 to 110°C.

Examples of commercially available styrene-(meth)acrylic copolymers include Joncryl ^RTM 67, 678, 680, 682, 683, 690, 52J, 57J, 60J, 63J, 70J, JDX-6180, HPD-196, HPD96J, PDX-6137A, 6610, JDX-6500, JDX-6639, PDX-6102B, and PDX-6124 (all manufactured by BASF). In this specification, the superscript RTM denotes a registered trademark. Among these, Joncryl 67 (mass average molecular weight: 12,500, acid value: 213 mg KOH/g), 678 (mass average molecular weight: 8,500, acid value: 215 mg KOH/g), 682 (mass average molecular weight: 1,700, acid value: 230 mg KOH/g), 683 (mass average molecular weight: 4,900, acid value: 215 mg KOH/g), 690 (mass average molecular weight: 16,500, acid value: 240 mg KOH/g), and the like are preferred, with Joncryl 678 being more preferred.

It is also preferred to use polyoxyethylene aryl phenyl ether-based dispersants and polyoxyethylene aryl phenyl ether sulfate-based dispersants as dispersants.

Examples of polyoxyethylene arylphenyl ether-based dispersants include styrylphenol compounds such as polyoxyethylene monostyrylphenyl ether, polyoxyethylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, and polyoxyethylene tetrastyrylphenyl ether; benzylphenol compounds such as polyoxyethylene monobenzylphenyl ether, polyoxyethylene dibenzylphenyl ether, and polyoxyethylene tribenzylphenyl ether; cumylphenol compounds such as polyoxyethylene cumylphenyl ether; polyoxyethylene naphthylphenyl ether, polyoxyethylene biphenyl ether, and polyoxyethylene phenoxyphenyl ether; and the like. Among these, polyoxyethylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, polyoxyethylene dibenzylphenyl ether, polyoxyethylene tribenzylphenyl ether, and polyoxyethylene cumylphenyl ether are preferred.

The number of repeats of the polyoxyethylene group in the polyoxyethylene aryl phenyl ether is preferably 1 to 30, and more preferably 15 to 30. If the number of repeats is 1 or more, the compatibility with aqueous solvents and the like tends to be excellent. Also, if the number of repeats is 30 or less, the viscosity tends not to become too high.

Commercially available styrylphenol compounds include, for example, Noigen EA series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); Paionin D-6112, Paionin D-6115, Paionin D-6120, Paionin D-6131, Paionin D-6512, Takesurf D-6413, DTD-51, Paionin D-6112, Paionin D-6320 (all manufactured by Takemoto Oil Co., Ltd.); TS-1500, TS-2000, TS-2600, SM-174N (all manufactured by Toho Chemical Industry Co., Ltd.); Emulgen A60, Emulgen A90, Emulgen A500 (all manufactured by Kao Corporation); and the like. Commercially available benzylphenol compounds include, for example, Emulgen B-66 (manufactured by Kao Corporation). Commercially available cumylphenol compounds include, for example, Newcol CMP series (manufactured by Nippon Nyukazai Co., Ltd.).

Examples of polyoxyethylene aryl phenyl ether sulfates include the sulfates of the polyoxyethylene aryl phenyl ethers described above.

Commercially available polyoxyethylene arylphenyl ether sulfate dispersants include, for example, SM-57, SM-130, and SM-210 (all manufactured by Toho Chemical Industry Co., Ltd.).

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

The content of the dispersant is preferably 1 to 200 parts by mass, and more preferably 7 to 140 parts by mass, per 100 parts by mass of the total of (A) the pigment, (B) the pigment derivative, and any other colorants that may be optionally contained.

[Additives]
The color dispersion liquid according to the present embodiment may contain additives other than those described above. Examples of additives include water-soluble organic solvents, preservatives, surfactants, pH adjusters, chelating agents, rust inhibitors, water-soluble UV absorbers, water-soluble polymer compounds, viscosity adjusters, dye dissolving agents, antioxidants, and resin emulsions. Among these, it is preferable to contain at least one selected from the group consisting of water-soluble organic solvents, preservatives, surfactants, and pH adjusters.

The content of the water-soluble organic solvent is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass, based on the total amount of the color dispersion. The content of other additives is preferably 0.1 to 5% by mass, and more preferably 0.2 to 2% by mass, based on the total amount of the color dispersion.

Examples of water-soluble organic solvents include glycol-based solvents, polyhydric alcohols, pyrrolidones, etc. Examples of glycol-based solvents include glycerin, polyglycerin (#310, #750, #800), diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, undecaglycerin, dodecaglycerin, tridecaglycerin, tetradecaglycerin, etc. Examples of polyhydric alcohols include C2-C6 polyhydric alcohols having 2 to 3 alcoholic hydroxyl groups; di- or tri-C2-C3 alkylene glycols; poly-C2-C3 alkylene glycols having 4 or more repeating units and a molecular weight of about 20,000 or less, preferably liquid polyalkylene glycols; and the like. Specific examples of these include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, thiodiglycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, glycerin, trimethylolpropane, 1,3-pentanediol, and 1,5-pentanediol. Examples of pyrrolidones include 2-pyrrolidone and N-methyl-2-pyrrolidone. For the sake of convenience, compounds that dissolve in water and act as wetting agents are also included in the water-soluble organic solvent. Examples of such compounds include urea, ethylene urea, and sugars.

Considering the storage stability of the colored dispersion liquid according to this embodiment, the water-soluble organic solvent is preferably a solvent in which the colorant has a low solubility, and it is particularly preferable to use glycerin in combination with a solvent other than glycerin (preferably a polyhydric alcohol other than glycerin).

Examples of preservatives include organic sulfur compounds, organic nitrogen sulfur compounds, organic halogen compounds, haloarylsulfone compounds, iodopropargyl compounds, N-haloalkylthio compounds, nitrile compounds, pyridine compounds, 8-oxyquinoline compounds, benzothiazole compounds, isothiazolin compounds, dithiols, pyridine oxide compounds, nitropropane compounds, organic tin compounds, phenol compounds, quaternary ammonium salt compounds, triazine compounds, thiazine compounds, anilides, adamantane compounds, dithiocarbamate compounds, brominated indanone compounds, benzyl bromoacetate compounds, inorganic salt compounds, and the like. A specific example of an organic halogen compound is sodium pentachlorophenol. A specific example of a pyridine oxide compound is sodium 2-pyridinethiol-1-oxide. Specific examples of isothiazoline compounds include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Specific examples of other antiseptics and fungicides include anhydrous sodium acetate, sodium sorbate, sodium benzoate, and trade names Proxel ^RTM GXL(S) and Proxel ^RTM XL-2(S) manufactured by Lonza.

Examples of surfactants include known surfactants such as anionic, cationic, amphoteric, nonionic, silicone, and fluorine-based 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 taurines, alkyl sulfates, polyoxyalkyl ether sulfates, alkyl sulfates, polyoxyethylene alkyl ether phosphates, rosin acid soaps, castor oil sulfates, lauryl alcohol sulfates, alkyl phenol phosphates, alkyl phosphates, alkylaryl sulfonates, diethyl sulfosuccinates, diethylhexyl sulfosuccinates, dioctyl sulfosuccinates, etc. Specific examples of commercially available products include Hitenol LA-10, LA-12, LA-16, Neo Hitenol ECL-30S, ECL-45, etc., all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

Examples of cationic surfactants include 2-vinylpyridine derivatives, poly-4-vinylpyridine derivatives, etc.

Examples of amphoteric surfactants include lauryl dimethylaminoacetate betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, coconut oil fatty acid amidopropyl dimethylaminoacetate betaine, polyoctyl polyaminoethyl glycine, imidazoline derivatives, etc.

Examples of nonionic surfactants include ether-based surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether; polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, and sorbitan sesquioleate. ester-based solvents such as polyoxyethylene oleate, polyoxyethylene stearate, etc.; acetylene glycol (alcohol)-based solvents such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3-ol, etc.; trade names of Surfynol 104, 105, 82, 465, Olfine STG, etc., manufactured by Air Products Japan Co., Ltd.; polyglycol ether-based solvents (for example, Tergitol 15-S-7, etc., manufactured by SIGMA-ALDRICH Corporation); and the like.

Examples of silicone surfactants include polyether-modified siloxanes and polyether-modified polydimethylsiloxanes. Specific examples of commercially available products include BYK-347 (polyether-modified siloxanes), BYK-345, and BYK-348 (polyether-modified polydimethylsiloxanes), all manufactured by BYK-Chemie.

Examples of fluorine-based surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups on the side chains, etc. Specific examples of commercially available products include Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30, FS-31 (all manufactured by DuPont); PF-151N, PF-154N (all manufactured by Omnova); etc.

Any substance can be used as the pH adjuster as long as it can control the pH of the color dispersion to a range of approximately 5 to 11 without adversely affecting the color dispersion to be prepared. Specific examples include alkanolamines such as diethanolamine, triethanolamine, and N-methyldiethanolamine; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonium hydroxide (aqueous ammonia); alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium bicarbonate, and potassium carbonate; alkali metal salts of organic acids such as potassium acetate; inorganic bases such as sodium silicate and disodium phosphate; and the like, with triethanolamine being preferred.

Specific examples of chelating agents include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracildiacetate, etc.

Examples of rust inhibitors include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, etc.

Examples of water-soluble UV absorbers include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, triazine compounds, etc.

Examples of water-soluble polymeric compounds include polyvinyl alcohol, cellulose derivatives, polyamines, polyimines, etc.

Viscosity adjusters include water-soluble organic solvents as well as water-soluble polymeric compounds, such as polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

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

As the antioxidant, for example, various organic and metal complex-based 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.

Examples of resin emulsions include emulsions formed from acrylic resins, epoxy resins, urethane resins, polyether resins, polyamide resins, unsaturated polyester resins, phenolic resins, silicone resins, fluororesins, polyvinyl resins (vinyl chloride, vinyl acetate, polyvinyl alcohol, etc.), alkyd resins, polyester resins, and amino materials (melamine resins, urea resins, urea resins, melamine formaldehyde resins, etc.). The resin emulsion may contain two or more types of resins. Two or more types of resins may form a core/shell structure. Among resin emulsions, urethane resin emulsions are preferred.

Urethane resin emulsions are commercially available, and many of them are emulsions with a solid content concentration of 30 to 60% by mass. Commercially available urethane resin emulsions include, for example, Permarin UA-150, 200, 310, 368, 3945, and U-coat UX-320 (all manufactured by Sanyo Chemical Industries, Ltd.); Hydran WLS-201, 210, and HW-312B latex (all manufactured by DIC Corporation); and Superflex 150, 170, and 470 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). Of these, examples of polycarbonate-based urethane resins include Permarin UA-310, 3945, and U-coat UX-320. Of these, examples of polyether-based urethane resins include Permarin UA-150, 200); and U-coat UX-340.

The urethane resin in the urethane resin emulsion preferably has an SP value of 8 to 24 (cal/cm ³ ) ^1/2 , more preferably 8 to 17 (cal/cm ³ ) ^1/2 , and even more preferably 8 to 11 (cal/cm ³ ) ^1/2 . The SP value of the urethane resin is calculated by the Fedors method. When the urethane resin has acidic groups and the emulsion is prepared by neutralizing these acidic groups, the SP value of the urethane resin before neutralization is used.

When the urethane resin in the urethane resin emulsion has acidic groups such as carboxy groups, sulfo groups, and hydroxy groups, the acidic groups may be converted to alkaline salts. For example, the acidic groups can be converted to alkaline salts by adding a urethane resin having acidic groups to water and stirring to prepare an aqueous solution, and then adding an alkaline compound to adjust the pH to 6.0 to 12.0. Examples of alkaline compounds include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metals such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide; and the like. The alkaline compounds may be used alone or in combination of two or more types.

[Method of preparing colored dispersion liquid, etc.]
An example of a method for preparing the colored dispersion liquid according to this embodiment is a method in which an aqueous dispersion liquid containing (A) the dye, (B) the dye derivative, and a dispersant is prepared, and an additive such as a water-soluble organic solvent is further added, as necessary.

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

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

From the viewpoint of high-speed ejection responsiveness, the viscosity of the colored dispersion liquid of this embodiment at 25°C is preferably about 3 to 20 mPa·s when measured with an E-type viscometer. Furthermore, the surface tension of the colored dispersion liquid of this embodiment at 25°C is preferably about 20 to 45 mN/m when measured with a plate method. In practice, the physical property values are adjusted to be appropriate, taking into consideration the ejection volume, response speed, and ink droplet flight characteristics of the inkjet printer used.

The color dispersion liquid according to this embodiment can be used in various fields and is suitable for aqueous writing inks, aqueous printing inks, information recording inks, textile printing, etc. It is particularly preferable to use the color dispersion liquid according to this embodiment as an inkjet textile printing ink.

The colored dispersion liquid according to this embodiment is unlikely to undergo solid precipitation, changes in physical properties, or color changes after long-term storage, and has excellent storage stability. In addition, it has good initial filling properties in inkjet printer heads and good continuous printing stability. Furthermore, there is almost no bleeding of the image on the recording medium after printing, making it possible to obtain a clear image.

In addition, the colored dispersion liquid of this embodiment can also be used as a colored dispersion liquid set in combination with other colored dispersion liquids of different color tones.

<Recording media>
The recording medium according to the present embodiment is a medium to which the color dispersion according to the present embodiment is attached. The recording medium is not particularly limited as long as it is capable of recording with the color dispersion according to the present embodiment, and examples thereof include fibers, paper (plain paper, inkjet paper, etc.). In particular, the recording medium according to the present embodiment is preferably a hydrophobic fiber to which the color dispersion according to the present embodiment is attached.

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

<Method of printing hydrophobic fibers>
The hydrophobic fiber printing method according to this embodiment is a method of printing a hydrophobic fiber using the color dispersion according to this embodiment described above. The hydrophobic fiber printing method is roughly divided into a direct printing method and a sublimation transfer method.

The direct printing method includes a printing process in which droplets of a colored dispersion are deposited on hydrophobic fibers using an inkjet printer to produce a recorded image such as letters or a picture, a fixing process in which the dye in the colored dispersion that was deposited on the hydrophobic fibers in the printing process is fixed to the hydrophobic fibers using heat, and a washing process in which any unfixed dye remaining in the hydrophobic fibers is washed away.

The fixing step is generally carried out by known steaming or baking. Examples of steaming include a method in which the hydrophobic fibers are treated with a high-temperature steamer, typically at 170-180°C for about 10 minutes, or with a high-pressure steamer, typically at 120-130°C for about 20 minutes, to fix the dye into the hydrophobic fibers (also called wet heat fixing). Examples of baking (thermosol) include a method in which the hydrophobic fibers are treated with a high-temperature steamer, typically at 190-210°C for about 6-120 seconds, to fix the dye into the hydrophobic fibers (also called dry heat fixing).

The washing step is a step in which the obtained fiber is washed with warm water and, if necessary, with water. The warm water or water used for washing may contain a surfactant. It is also preferable to dry the hydrophobic fiber after washing, usually at 50 to 120°C, for 5 to 30 minutes.

On the other hand, the sublimation transfer method includes a printing process in which droplets of a colored dispersion are deposited on an intermediate recording medium using an inkjet printer to obtain a recorded image such as letters or a picture, and a transfer process in which the recorded image is transferred to the hydrophobic fiber by contacting the surface of the intermediate recording medium on which the colored dispersion has been deposited with hydrophobic fiber and then subjecting it to heat treatment.

It is preferable for the intermediate recording medium to be one in which the dye in the applied color dispersion does not aggregate on its surface and does not interfere with the sublimation of the dye when the recorded image is transferred to the hydrophobic fiber. One example of such an intermediate recording medium is paper with an ink-receiving layer formed on the surface using inorganic fine particles such as silica, and specialized paper for inkjet printing can be used.

The heat treatment used in the transfer process typically involves dry heat treatment at around 190 to 200°C.

The hydrophobic fiber printing method according to this embodiment may further include a pretreatment step for the hydrophobic fiber to prevent bleeding, etc. This pretreatment step may include a step of applying an aqueous solution (pretreatment liquid) containing a paste material, an alkaline substance, a reduction inhibitor, and a hydrotropic agent to the hydrophobic fiber before the coloring dispersion liquid is applied.

Examples of adhesives include natural gums such as guar and locust bean; starches; seaweeds such as sodium alginate and funori; plant skins such as pectinic acid; cellulose derivatives such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose; processed starches such as carboxymethyl starch; synthetic glues such as polyvinyl alcohol and polyacrylic esters; and the like, with sodium alginate being preferred.

Examples of alkaline substances include alkali metal salts of inorganic or organic acids, salts of alkaline earth metals, compounds that liberate alkali when heated, and the like, with alkali metal hydroxides and alkali metal salts being preferred. Specific examples include alkali metal hydroxides such as sodium hydroxide and calcium hydroxide, alkali metal salts of inorganic compounds such as sodium carbonate, sodium bicarbonate, 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, with sodium bicarbonate being preferred.

As the reduction inhibitor, sodium metanitrobenzenesulfonate is preferred.
Examples of the hydrotropic agent include urea compounds such as urea and dimethylurea, with urea being preferred.

The adhesive, alkaline substance, reduction inhibitor, and hydrotropic agent may be used alone or in combination of two or more.

The mixing ratio of each component in the pretreatment liquid is, for example, 0.5 to 5 mass% adhesive, 0.5 to 5 mass% sodium bicarbonate, 0 to 5 mass% sodium metanitrobenzenesulfonate, 1 to 20 mass% urea, and the remainder water.

One method for applying the pretreatment liquid to hydrophobic fibers is the padding method. The padding squeeze rate is preferably about 40 to 90%, and more preferably about 60 to 80%.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means parts by mass and "%" means % by mass. The aqueous dispersions and inks using the same in each example are all included in the above-mentioned colored dispersions.

<Preparation Example 1: Preparation of NaOH neutralized product of Joncryl 678>
Joncryl 678 (manufactured by BASF) (20 parts) was added to a mixture of 25% sodium hydroxide (6 parts), ion-exchanged water (54 parts), and propylene glycol (20 parts), and the mixture was heated to 90 to 120° C. and stirred for 5 hours to obtain a NaOH neutralized product of Joncryl 678.

<Preparation Example 2: Preparation of NaOH neutralized product of Joncryl JDX-300C>
Joncryl JDX-300C (manufactured by BASF) (20 parts) was added to a mixture of 25% sodium hydroxide (6 parts), ion-exchanged water (54 parts), and propylene glycol (20 parts), and the mixture was heated to 90 to 120° C. and stirred for 5 hours to obtain a NaOH neutralized product of Joncryl JDX-300C.

<Examples 1a to 29a: Preparation of aqueous dispersions 1a to 29a>
Glass beads with a diameter of 0.2 mm were added to a mixture of each component shown in Tables 1 to 4 below, and the mixture was dispersed in a sand mill for about 30 hours under water cooling. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC Corporation) to obtain aqueous dispersions 1a to 29a.

Comparative Examples 1a to 9a: Preparation of Aqueous Dispersions 30a to 38a
Glass beads with a diameter of 0.2 mm were added to a mixture of each component shown in Table 5 below, and the mixture was dispersed in a sand mill for about 30 hours under water cooling. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to obtain aqueous dispersions 30a to 38a.

The numerical values of each component in Tables 1 to 5 represent parts by mass. The abbreviations in Tables 1 to 5 represent the following:
DB359: C.I. Disperse Blue 359
SB35: C.I. Solvent Blue 35
SB36: C.I. Solvent Blue 36
SB78: C.I. Solvent Blue 78
SB102: C.I. Solvent Blue 102
SB105: C.I. Solvent Blue 105
SB112: C.I. Solvent Blue 112
SB12: C.I. Solvent Blue 12
SB13: C.I. Solvent Blue 13
SB58: C.I. Solvent Blue 58
SB63: C.I. Solvent Blue 63
SB83: C.I. Solvent Blue 83
SB86: C.I. Solvent Blue 86
SB94: C.I. Solvent Blue 94
SB111: C.I. Solvent Blue 111
TS-2000: Polyoxyethylene styryl phenyl ether dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
SM-57: Polyoxyethylene styryl phenyl ether sulfate dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
Labellin W-40: Creosote oil sodium sulfonate formalin condensate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Labelin FD-40: sodium naphthalenesulfonate formalin condensate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Labelin MN-40: Sodium methylnaphthalenesulfonate formalin condensate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Demol SC-30: Sodium meta-cresol sulfonate formalin condensate (manufactured by Kao Corporation)
Morwet D425: Sodium alkylnaphthalenesulfonate formalin condensate (manufactured by Lion Specialty Chemicals Co., Ltd.)
Zetasperse 3100: Polymer resin dispersant (Evonik Japan Co., Ltd.)
BYK-190: Polymer resin dispersant (manufactured by BYK Japan Co., Ltd.)
BYK-2015: Polymer resin dispersant (manufactured by BYK Japan Co., Ltd.)
TEGODISPER 755W: Polymer resin dispersant (manufactured by Evonik Japan Co., Ltd.)
Solsperse 46000: Polymer resin dispersant (manufactured by Lubrizol Japan, Ltd.)
Solsperse J400: Polymer resin dispersant (manufactured by Lubrizol Japan, Ltd.)
TS-1500: Polyoxyethylene styryl phenyl ether dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
SM-210: Polyoxyethylene styryl phenyl ether sulfate dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
Nikkol BPS-30: ethylene oxide adduct of phytosterol (manufactured by Nikko Chemicals Co., Ltd.)
Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza)
Surfynol 104PG50: Surfynol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted with propylene glycol to a concentration of 50%.

Examples 30a to 58a: Preparation of Inks 1a to 29a
The aqueous dispersions 1a to 29a obtained in Examples 1a to 29a were mixed with the components shown in Tables 6 to 9 below, stirred for 30 minutes, and then filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to prepare inks 1a to 29a, respectively.

Comparative Examples 10a to 18a: Preparation of Inks 30a to 38a
The aqueous dispersions 30a to 38a obtained in Comparative Examples 1a to 9a were mixed with the components shown in Table 10 below, stirred for 30 minutes, and then filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to prepare inks 30a to 38a, respectively.

The numerical values of each component in Tables 6 to 10 represent parts by mass. The abbreviations in Tables 6 to 10 represent the following:
BYK-348: Polyether-modified polydimethylsiloxane (manufactured by BYK Japan Co., Ltd.)
TEA-80: Triethanolamine (manufactured by Oxalis Chemicals Co., Ltd.)
Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza)

<Examples 59a to 64a and Comparative Example 19a: Preparation of aqueous dispersions 39a to 45a>
Glass beads with a diameter of 0.2 mm were added to a mixture of each component shown in Table 11 below, and the mixture was dispersed in a sand mill for about 30 hours under water cooling. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to obtain aqueous dispersions 39a to 45a.

The numerical values of each component in Table 11 represent parts by mass. The abbreviations in Table 11 have the same meanings as in Tables 1 to 5.

<Preparation of Examples 65a to 70a and Comparative Examples 20a to 21a: Inks 39a to 46a>
The aqueous dispersions 30a, 39a to 45a obtained in Comparative Example 1a, Examples 59a to 64a, and Comparative Example 19a were mixed with the components shown in Table 12 below, stirred for 30 minutes, and then filtered through glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to prepare inks 39a to 46a, respectively.

The numerical values of each component in Table 12 represent parts by mass. The abbreviations in Table 12 have the same meanings as in Tables 6 to 10.

<Evaluation>
The aqueous dispersions 1a to 45a and inks 1a to 46a prepared as described above were used to carry out the following evaluation tests. The results are shown in Tables 1 to 12.

[Particle size change test]
The median diameter (D50, number average particle diameter) of the colorant in each aqueous dispersion or ink stored at 60° C. for 5 days was measured using a MICRO TRAC UPA EX150 (manufactured by Microtrac Corporation) and evaluated according to the following criteria: A or B indicates good storage stability, and C or D indicates poor storage stability.
-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

[Sedimentation test]
The sedimentation rate was calculated according to the following formula using the absorbance Abs ₀ at the maximum absorption wavelength (λmax) near 574 nm measured when the ink was prepared, and the absorbance Abs ₁ at the maximum absorption wavelength (λmax) near 574 nm measured by taking an aliquot of the supernatant of the ink stored at 60° C. for 5 days. The absorbance was measured using an ultraviolet-visible spectrophotometer (UV-2550, manufactured by Shimadzu Corporation) after diluting the ink 2000 times with ion-exchanged water.
Sedimentation rate (%)={(Abs ₀ −Abs ₁ )/Abs ₀ }×100
The calculated sedimentation rate was evaluated according to the following criteria: A or B indicates good storage stability, and C indicates poor storage stability.
-Evaluation criteria-
A: Sedimentation rate is less than 5%. B: Sedimentation rate is 5% or more and less than 15%. C: Sedimentation rate is 15% or more.

[Redispersibility test]
25 μL of each aqueous dispersion or ink was dropped onto a glass petri dish and dried for 1 hour in a thermostatic chamber at 60° C. 10 mL of ion-exchanged water was dropped onto the resulting dried product at room temperature, and the product was visually observed to see whether it redispersed or not, and evaluated according to the following four-level criteria. The more the ink redisperses, the easier it is to eliminate clogging after drying, and therefore the better it is. A, B, or C indicates good redispersibility, and D indicates poor redispersibility.
-Evaluation criteria-
A: No residue was left and the entire product was redispersed.
B: A small amount of residue remains, but most has been redispersed.
C: A large amount of residue remains, but is somewhat redispersed.
D: Not redispersed at all.

As is clear from the results in Tables 1 to 12 above, the aqueous dispersions of Examples 1a to 29a and 59a to 64a, and the inks of Examples 30a to 58a and 65a to 70a prepared using them, all had excellent storage stability, with few coarse particles, and good sedimentation properties, as the particle size did not increase significantly when stored at high temperatures. On the other hand, the aqueous dispersions of Comparative Examples 1a to 9a and 19a, and the inks of Comparative Examples 10a to 18a and 20a to 21a prepared using them, had inferior storage stability compared to the Examples.

Furthermore, the evaluation results of the aqueous dispersions of Examples 1a to 7a, 24a to 29a, and 59a to 64a, and the inks prepared using them of Examples 30a to 36a, 53a to 58a, and 65a to 70a, showed that redispersibility was improved by using a polyoxyethylene arylphenyl ether sulfate-based dispersant as a dispersant.

<Examples 1b to 29b: Preparation of aqueous dispersions 1b to 29b>
Glass beads with a diameter of 0.2 mm were added to a mixture of each component shown in Tables 13 to 16 below, and the mixture was dispersed in a sand mill for about 30 hours under water cooling. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC Corporation) to obtain aqueous dispersions 1b to 29b.

<Comparative Examples 1b to 9b: Preparation of Aqueous Dispersions 30b to 38b>
Glass beads with a diameter of 0.2 mm were added to a mixture of each component shown in Table 17 below, and the mixture was dispersed in a sand mill for about 30 hours under water cooling. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC Corporation) to obtain aqueous dispersions 30b to 38b.

The numerical values of each component in Tables 13 to 17 represent parts by mass. The abbreviations in Tables 13 to 17 represent the following:
DY54: C.I. Disperse Yellow 54
DY64: C.I. Disperse Yellow 64
DY134: C.I. Disperse Yellow 134
DY143: C.I. Disperse Yellow 143
DY149: C.I. Disperse Yellow 149
DY160: C.I. Disperse Yellow 160
DY1: C.I. Disperse Yellow 1
DY9: C.I. Disperse Yellow 9
DY31: C.I. Disperse Yellow 31
DY33: C.I. Disperse Yellow 33
DY104: C.I. Disperse Yellow 104
DY119: C.I. Disperse Yellow 119
DY126: C.I. Disperse Yellow 126
TS-2000: Polyoxyethylene styryl phenyl ether dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
SM-57: Polyoxyethylene styryl phenyl ether sulfate dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
Labellin W-40: Creosote oil sodium sulfonate formalin condensate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Labelin FD-40: sodium naphthalenesulfonate formalin condensate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Labelin MN-40: Sodium methylnaphthalenesulfonate formalin condensate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Demol SC-30: Sodium meta-cresol sulfonate formalin condensate (manufactured by Kao Corporation)
Morwet D425: Sodium alkylnaphthalenesulfonate formalin condensate (manufactured by Lion Specialty Chemicals Co., Ltd.)
Zetasperse 3100: Polymer resin dispersant (Evonik Japan Co., Ltd.)
BYK-190: Polymer resin dispersant (manufactured by BYK Japan Co., Ltd.)
BYK-2015: Polymer resin dispersant (manufactured by BYK Japan Co., Ltd.)
TEGODISPER 755W: Polymer resin dispersant (manufactured by Evonik Japan Co., Ltd.)
Solsperse 46000: Polymer resin dispersant (manufactured by Lubrizol Japan, Ltd.)
Solsperse J400: Polymer resin dispersant (manufactured by Lubrizol Japan, Ltd.)
TS-1500: Polyoxyethylene styryl phenyl ether dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
SM-210: Polyoxyethylene styryl phenyl ether sulfate dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
Nikkol BPS-30: ethylene oxide adduct of phytosterol (manufactured by Nikko Chemicals Co., Ltd.)
Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza)
Surfynol 104PG50: Surfynol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted with propylene glycol to a concentration of 50%.

Examples 30b to 58b: Preparation of Inks 1b to 29b
The aqueous dispersions 1b to 29b obtained in Examples 1b to 29b were mixed with the components shown in Tables 18 to 21 below, stirred for 30 minutes, and then filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to prepare inks 1b to 29b, respectively.

Comparative Examples 10b to 18b: Preparation of Inks 30b to 38b
The aqueous dispersions 30b to 38b obtained in Comparative Examples 1b to 9b were mixed with the components shown in Table 22 below, stirred for 30 minutes, and then filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to prepare inks 30b to 38b, respectively.

The numerical values of each component in Tables 18 to 22 represent parts by mass. The abbreviations in Tables 18 to 22 represent the following:
BYK-348: Polyether-modified polydimethylsiloxane (manufactured by BYK Japan Co., Ltd.)
TEA-80: Triethanolamine (manufactured by Oxalis Chemicals Co., Ltd.)
Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza)

<Examples 59b to 64b and Comparative Example 19b: Preparation of aqueous dispersions 39b to 45b>
Glass beads with a diameter of 0.2 mm were added to a mixture of each component shown in Table 23 below, and the mixture was dispersed in a sand mill for about 30 hours under water cooling. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC Corporation) to obtain aqueous dispersions 39b to 45b.

The numerical values of each component in Table 23 represent parts by mass. The abbreviations in Table 23 have the same meanings as in Tables 13 to 17.

<Preparation of Examples 65b to 70b and Comparative Examples 20b to 21b: Inks 39b to 46b>
The aqueous dispersions 38b to 45b obtained in Comparative Example 9b, Examples 59b to 64b, and Comparative Example 19b were mixed with the components shown in Table 24 below, stirred for 30 minutes, and then filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to prepare inks 39b to 46b, respectively.

The numerical values of each component in Table 24 represent parts by mass. The abbreviations in Table 24 have the same meanings as in Tables 18 to 22.

<Evaluation>
The aqueous dispersions 1b to 45b and inks 1b to 46b prepared as described above were used to carry out the following evaluation tests. The results are shown in Tables 13 to 22.

[Particle size change test]
The median diameter (D50, number average particle diameter) of the colorant in each aqueous dispersion or ink stored at 60° C. for 5 days was measured using a MICRO TRAC UPA EX150 (manufactured by Microtrac Corporation) and evaluated according to the following criteria: A or B indicates good storage stability, and C or D indicates poor storage stability.
-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

[Sedimentation test]
The sedimentation rate was calculated according to the following formula using the absorbance Abs ₀ at the maximum absorption wavelength (λmax) near 408 nm measured when the ink was prepared, and the absorbance Abs ₁ at the maximum absorption wavelength (λmax) near 408 nm measured by taking an aliquot of the supernatant of the ink stored at 60° C. for 5 days. The absorbance was measured using an ultraviolet-visible spectrophotometer (UV-2550, manufactured by Shimadzu Corporation) after diluting the ink 2000 times with ion-exchanged water.
Sedimentation rate (%)={(Abs ₀ −Abs ₁ )/Abs ₀ }×100
The calculated sedimentation rate was evaluated according to the following criteria: A or B indicates good storage stability, and C indicates poor storage stability.
-Evaluation criteria-
A: Sedimentation rate is less than 5%. B: Sedimentation rate is 5% or more and less than 15%. C: Sedimentation rate is 15% or more.

[Redispersibility test]
25 μL of each aqueous dispersion or ink was dropped onto a glass petri dish and dried for 1 hour in a thermostatic chamber at 60° C. 10 mL of ion-exchanged water was dropped onto the resulting dried product at room temperature, and the product was visually observed to see whether it redispersed or not, and evaluated according to the following four-level criteria. The more the ink redisperses, the easier it is to eliminate clogging after drying, and therefore the better it is. A, B, or C indicates good redispersibility, and D indicates poor redispersibility.
-Evaluation criteria-
A: No residue was left and the entire product was redispersed.
B: A small amount of residue remains, but most has been redispersed.
C: A large amount of residue remains, but is somewhat redispersed.
D: Not redispersed at all.

As is clear from the results in Tables 13 to 22 above, the aqueous dispersions of Examples 1b to 29b and 59b to 64b, and the inks of Examples 30b to 58b and 65b to 70b prepared using them, did not increase significantly in particle size during high-temperature storage, so had few coarse particles, good sedimentation properties, and excellent storage stability. On the other hand, the aqueous dispersions of Comparative Examples 1b to 9b and 19b, and the inks of Comparative Examples 10b to 18b and 20b to 21b prepared using them, had inferior storage stability compared to the Examples.

Furthermore, the evaluation results of the aqueous dispersions of Examples 1b to 7b, 24b to 29b, and 59b to 64b, and the inks prepared using them of Examples 30b to 36b, 53b to 58b, and 65b to 70b, showed that redispersibility was improved by using a polyoxyethylene arylphenyl ether sulfate-based dispersant as a dispersant.

<Examples 1c to 28c: Preparation of aqueous dispersions 1c to 28c>
Glass beads with a diameter of 0.2 mm were added to a mixture of each component shown in Tables 25 to 28 below, and the mixture was dispersed in a sand mill for about 30 hours under water cooling. The resulting solution was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC Corporation) to obtain aqueous dispersions 1c to 28c.

Comparative Examples 1c to 11c: Preparation of Aqueous Dispersions 29c to 39c
Glass beads with a diameter of 0.2 mm were added to a mixture of each component shown in Table 29 below, and the mixture was dispersed in a sand mill for about 30 hours under water cooling. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC Corporation) to obtain aqueous dispersions 29c to 39c.

The numerical values of each component in Tables 25 to 29 represent parts by mass. The abbreviations in Tables 25 to 29 represent the following:
SO60: C.I. Solvent Orange 60
SR179: C.I. Solvent Red 179
SR180: C.I. Solvent Red 180
DO118: C.I. Disperse Orange 118
DO25: C.I. Disperse Orange 25
DO56: C.I. Disperse Orange 56
DO73: C.I. Disperse Orange 73
DR60: C.I. Disperse Red 60
DY54: C.I. Disperse Yellow 54
TS-2000: Polyoxyethylene styryl phenyl ether dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
SM-57: Polyoxyethylene styryl phenyl ether sulfate dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
Labellin W-40: Creosote oil sodium sulfonate formalin condensate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Labelin FD-40: sodium naphthalenesulfonate formalin condensate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Labelin MN-40: Sodium methylnaphthalenesulfonate formalin condensate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Demol SC-30: Sodium meta-cresol sulfonate formalin condensate (manufactured by Kao Corporation)
Morwet D425: Sodium alkylnaphthalenesulfonate formalin condensate (manufactured by Lion Specialty Chemicals Co., Ltd.)
Zetasperse 3100: Polymer resin dispersant (Evonik Japan Co., Ltd.)
BYK-190: Polymer resin dispersant (manufactured by BYK Japan Co., Ltd.)
BYK-2015: Polymer resin dispersant (manufactured by BYK Japan Co., Ltd.)
TEGODISPER 755W: Polymer resin dispersant (manufactured by Evonik Japan Co., Ltd.)
Solsperse 46000: Polymer resin dispersant (manufactured by Lubrizol Japan, Ltd.)
Solsperse J400: Polymer resin dispersant (manufactured by Lubrizol Japan, Ltd.)
TS-1500: Polyoxyethylene styryl phenyl ether dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
SM-210: Polyoxyethylene styryl phenyl ether sulfate dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
Nikkol BPS-30: ethylene oxide adduct of phytosterol (manufactured by Nikko Chemicals Co., Ltd.)
Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza)
Surfynol 104PG50: Surfynol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted with propylene glycol to a concentration of 50%.

Examples 29c to 56c: Preparation of Inks 1c to 28c
The aqueous dispersions 1c to 28c obtained in Examples 1c to 28c were mixed with the components shown in Tables 30 to 33 below, stirred for 30 minutes, and then filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to prepare inks 1c to 28c, respectively.

Comparative Examples 12c to 22c: Preparation of Inks 29c to 39c
The aqueous dispersions 29c to 39c obtained in Comparative Examples 1c to 11c were mixed with the components shown in Table 34 below, stirred for 30 minutes, and then filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to prepare inks 29c to 39c, respectively.

The numerical values of each component in Tables 30 to 34 represent parts by mass. The abbreviations in Tables 30 to 34 represent the following:
BYK-348: Polyether-modified polydimethylsiloxane (manufactured by BYK Japan Co., Ltd.)
TEA-80: Triethanolamine (manufactured by Oxalis Chemicals Co., Ltd.)
Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza)

<Examples 57c to 63c and Comparative Example 23c: Preparation of aqueous dispersions 40c to 47c>
Glass beads with a diameter of 0.2 mm were added to a mixture of each component shown in Table 35 below, and the mixture was dispersed in a sand mill for about 30 hours under water cooling. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by ADVANTEC Corporation) to obtain aqueous dispersions 40c to 47c.

The numerical values of each component in Table 35 represent parts by mass. The abbreviations in Table 35 have the same meanings as in Tables 25 to 29.

Preparation of Examples 64c to 70c and Comparative Examples 24c to 25c: Inks 40c to 48c
The aqueous dispersions 29c, 40c to 47c obtained in Comparative Example 1c, Examples 57c to 63c, and Comparative Example 23c were mixed with the components shown in Table 36 below, stirred for 30 minutes, and then filtered through glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to prepare inks 40c to 48c, respectively.

The numerical values of each component in Table 36 represent parts by mass. The abbreviations in Table 36 have the same meanings as in Tables 30 to 34.

<Evaluation>
The aqueous dispersions 1c to 47c and inks 1c to 48c prepared as above were used to carry out the following evaluation tests. The results are shown in Tables 25 to 36 above.

[Particle size change test]
The median diameter (D50, number average particle diameter) of the colorant in each aqueous dispersion or ink stored at 60° C. for 5 days was measured using a MICRO TRAC UPA EX150 (manufactured by Microtrac Corporation) and evaluated according to the following criteria: A or B indicates good storage stability, and C or D indicates poor storage stability.
-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

[Sedimentation test]
The sedimentation rate was calculated according to the following formula using the absorbance Abs ₀ at the maximum absorption wavelength (λmax) near 495 nm measured when the ink was prepared, and the absorbance Abs ₁ at the maximum absorption wavelength (λmax) near 495 nm measured by taking an aliquot of the supernatant of the ink stored at 60° C. for 5 days. The absorbance was measured using an ultraviolet-visible spectrophotometer (UV-2550, manufactured by Shimadzu Corporation) after diluting the ink 500-fold with ion-exchanged water.
Sedimentation rate (%)={(Abs ₀ −Abs ₁ )/Abs ₀ }×100
The calculated sedimentation rate was evaluated according to the following criteria: A or B indicates good storage stability, and C indicates poor storage stability.
-Evaluation criteria-
A: Sedimentation rate is less than 5%. B: Sedimentation rate is 5% or more and less than 15%. C: Sedimentation rate is 15% or more.

[Redispersibility test]
25 μL of each aqueous dispersion or ink was dropped onto a glass petri dish and dried for 1 hour in a thermostatic chamber at 60° C. 10 mL of ion-exchanged water was dropped onto the resulting dried product at room temperature, and the product was visually observed to see whether it redispersed or not, and evaluated according to the following four-level criteria. The more the ink redisperses, the easier it is to eliminate clogging after drying, and therefore the better it is. A, B, or C indicates good redispersibility, and D indicates poor redispersibility.
-Evaluation criteria-
A: No residue was left and the entire product was redispersed.
B: A small amount of residue remains, but most has been redispersed.
C: A large amount of residue remains, but is somewhat redispersed.
D: Not redispersed at all.

As is clear from the results in Tables 25 to 36 above, the aqueous dispersions of Examples 1c to 28c, 57c to 63c, and the inks of Examples 29c to 56c, 64c to 70c prepared using them all showed no significant increase in particle size during high-temperature storage, so had few coarse particles, good sedimentation properties, and excellent storage stability. On the other hand, the aqueous dispersions of Comparative Examples 1c to 11c, 23c, and the inks of Comparative Examples 12c to 22c, 24c to 25c prepared using them had inferior storage stability compared to the Examples.

Furthermore, the evaluation results of the aqueous dispersions of Examples 1c to 6c, 23c to 28c, and 57c to 63c, and the inks prepared using them of Examples 29c to 34c, 51c to 56c, and 64c to 70c, showed that redispersibility was improved by using a polyoxyethylene arylphenyl ether sulfate-based dispersant as a dispersant.

Synthesis Example 1: Synthesis of compound represented by formula (10)
(Step 1: Synthesis of compound represented by formula (20))
m-Chloroaniline (6.4 parts), potassium carbonate (13.8 parts), and iodoethane (18.7 parts) were added to N,N-dimethylformamide (30 parts), and the mixture was heated to 100° C. and reacted for 6 hours. The mixture was cooled to 60° C., and water (100 parts) was added to the resulting reaction liquid, followed by extraction three times with toluene (50 parts). The resulting organic layer was washed three times with water (100 parts), after which the toluene was removed using an evaporator, and the mixture was dried to obtain a compound (10 parts) represented by the following formula (20).

(Step 2: Synthesis of compound represented by formula (10))
2-Ethyl-4-nitroaniline (4.1 parts) was added to 96% sulfuric acid (20 parts), and the mixture was stirred at 30 to 40°C for 30 minutes to dissolve. After cooling to 5°C or less in an ice-water bath, 43% nitrosyl nitrate (7.2 parts) was added at the same temperature and stirred for 1 hour to synthesize a diazonium salt. The compound represented by the above formula (20) obtained in the above (step 1) (14.6 parts) was added to 50% aqueous methanol (100 parts) and stirred for 30 minutes at 5°C or less. The diazonium salt solution prepared above was added to this liquid, and the pH was adjusted to 2.0 with 25% liquid caustic soda, and the mixture was reacted for 3 hours under conditions of pH 2.0 to 2.5 and 0 to 10°C. After the reaction was completed, the mixture was filtered and washed with water to obtain a compound represented by the following formula (13) (10.2 parts).

Synthesis Example 2: Synthesis of compound represented by formula (11)
2-Amino-5-nitrothiazole (6.9 parts) was added to 96% sulfuric acid (30 parts), and the mixture was stirred at 30 to 40°C for 30 minutes to dissolve. After cooling to 5°C or less in an ice-water bath, 43% nitrosyl nitrate (17 parts) was added at the same temperature and stirred for 1 hour to synthesize a diazonium salt. The compound represented by the above formula (20) obtained in (Step 1) of Synthesis Example 1 above (7.6 parts) was added to 50% aqueous methanol (100 parts) and stirred for 30 minutes at 5°C or less. The diazonium salt solution prepared above was added to this liquid, and the pH was adjusted to 2.0 with 25% liquid caustic soda, and the mixture was reacted for 3 hours under conditions of pH 2.0 to 2.5 and 0 to 10°C. After the reaction was completed, the mixture was filtered and washed with water to obtain a compound represented by the following formula (11) (6.2 parts).

Synthesis Example 3: Synthesis of compound represented by formula (12)
2-Methyl-4-nitroaniline (16.7 parts) and 35% hydrochloric acid (34.4 parts) were added to ice water (100 parts) and stirred at 0 to 10°C for 30 minutes. At the same temperature, 40% sodium nitrite (19.9 parts) was added and stirred for 1 hour. The compound represented by the above formula (20) (18.2 parts) obtained in (Step 1) of Synthesis Example 1 was added to the obtained reaction liquid and reacted for 2 hours under conditions of pH 2.0 to pH 2.5 and 0 to 10°C, and 2 hours under conditions of pH 3.0 to 3.5 and 0 to 10°C. After the reaction was completed, the mixture was filtered and washed with water to obtain a compound represented by formula (12) (19.2 parts).

Synthesis Example 4: Synthesis of compound represented by formula (13)
2,4,6-trichloroaniline (8.0 parts) was added to 96% sulfuric acid (50 parts), and the mixture was stirred at 30 to 40°C for 30 minutes to dissolve. After cooling to 5°C or less in an ice-water bath, 43% nitrosyl nitrate (12 parts) was added at the same temperature and stirred for 1 hour to synthesize a diazonium salt. N,N-diethyl-m-toluidine (6.6 parts) was added to 50% aqueous methanol (100 parts), and the mixture was stirred at 5°C or less for 30 minutes. The diazonium salt solution prepared above was added to this liquid, and the pH was adjusted to 2.0 with 25% liquid caustic soda, and the reaction was carried out for 3 hours under conditions of pH 2.0 to 2.5 and 0 to 10°C. After the reaction was completed, the mixture was filtered and washed with water to obtain a compound represented by the following formula (13) (12.2 parts).

Synthesis Example 5: Synthesis of compound represented by formula (14)
p-Nitroaniline (8.2 parts) and 35% hydrochloric acid (18.8 parts) were added to ice water (50 parts) and stirred at 0 to 10°C for 30 minutes. At the same temperature, 40% sodium nitrite (10.9 parts) was added and stirred for 1 hour. The compound represented by the above formula (20) (10 parts) obtained in (Step 1) of Synthesis Example 1 was added to the obtained reaction liquid and reacted for 2 hours under conditions of pH 2.0 to 2.5 and 0 to 10°C, and 2 hours under conditions of pH 3.0 to 3.5 and 0 to 10°C. After the reaction was completed, the mixture was filtered and washed with water to obtain a compound represented by the following formula (14) (15.0 parts).

Synthesis Example 6: Synthesis of compound represented by formula (15)
(Step 1: Synthesis of compound represented by formula (21))
m-Bromoaniline (8.6 parts), potassium carbonate (13.8 parts), and iodoethane (18.7 parts) were added to N,N-dimethylformamide (30 parts), and the mixture was heated to 100° C. and reacted for 6 hours. The mixture was cooled to 60° C., and water (100 parts) was added to the resulting reaction liquid, followed by extraction three times with toluene (50 parts). The resulting organic layer was washed three times with water (100 parts), and then the toluene was removed using an evaporator, followed by drying to obtain a compound (11 parts) represented by the following formula (21).

(Step 2: Synthesis of compound represented by formula (15))
p-Nitroaniline (8.2 parts) and 35% hydrochloric acid (18.8 parts) were added to ice water (50 parts) and stirred at 0 to 10°C for 30 minutes. At the same temperature, 40% sodium nitrite (10.9 parts) was added and stirred for 1 hour. The compound represented by the above formula (21) (11 parts) obtained in the above (step 1) was added to the obtained reaction liquid and reacted for 2 hours under conditions of pH 2.0 to 2.5 and 0 to 10°C, and 2 hours under conditions of pH 3.0 to 3.5 and 0 to 10°C. After the reaction was completed, the mixture was filtered and washed with water to obtain a compound represented by the following formula (15) (14.0 parts).

Synthesis Example 7: Synthesis of compound represented by formula (16)
2,6-dichloro-p-nitroaniline (12.4 parts) was added to 96% sulfuric acid (60 parts), and the mixture was stirred at 30 to 40°C for 30 minutes to dissolve. After cooling to 5°C or less in an ice-water bath, 43% nitrosyl nitrate (9.2 parts) was added at the same temperature and stirred for 1 hour to synthesize a diazonium salt. The compound represented by the above formula (20) obtained in (Step 1) of Synthesis Example 1 above (9.0 parts) was added to 50% aqueous methanol (100 parts) and stirred for 30 minutes at 5°C or less. The diazonium salt solution prepared above was added to this liquid, and the pH was adjusted to 2.0 with 25% liquid caustic soda, and the mixture was reacted for 3 hours under conditions of pH 2.0 to 2.5 and 0 to 10°C. After the reaction was completed, the mixture was filtered and washed with water to obtain a compound represented by the following formula (16) (14.2 parts).

Synthesis Example 8: Synthesis of compound represented by formula (17)
2-aminothiazole (4 parts) was added to 96% sulfuric acid (35 parts), and the mixture was stirred at 30 to 40°C for 30 minutes to dissolve. After cooling to 5°C or less in an ice-water bath, 43% nitrosyl nitrate (6.1 parts) was added at the same temperature and stirred for 1 hour to synthesize a diazonium salt. The compound represented by the above formula (20) obtained in (Step 1) of Synthesis Example 1 above (9.0 parts) was added to 50% aqueous methanol (100 parts) and stirred for 30 minutes at 5°C or less. The diazonium salt solution prepared above was added to this liquid, and the pH was adjusted to 2.0 with 25% liquid caustic soda, and the mixture was reacted for 3 hours under conditions of pH 2.0 to 2.5 and 0 to 10°C. After the reaction was completed, the mixture was filtered and washed with water to obtain a compound represented by the following formula (17) (5.0 parts).

Synthesis Example 9: Synthesis of compound represented by formula (18)
3-Chloro-4-nitroaniline (5 parts) was added to 96% sulfuric acid (45 parts), and the mixture was stirred at 30 to 40°C for 30 minutes to dissolve. After cooling to 5°C or less in an ice-water bath, 43% nitrosyl nitrate (9.4 parts) was added at the same temperature and stirred for 1 hour to synthesize a diazonium salt. The compound represented by the above formula (20) obtained in (Step 1) of Synthesis Example 1 above (9.0 parts) was added to 50% aqueous methanol (100 parts) and stirred for 30 minutes at 5°C or less. The diazonium salt solution prepared above was added to this liquid, and the pH was adjusted to 2.0 with 25% liquid caustic soda, and the reaction was carried out for 3 hours under conditions of pH 2.0 to 2.5 and 0 to 10°C. After the reaction was completed, the mixture was filtered and washed with water to obtain a compound represented by the following formula (18) (6.9 parts).

<Examples 1d to 29d: Preparation of aqueous dispersions 1d to 29d>
Glass beads with a diameter of 0.2 mm were added to a mixture of each component shown in Tables 37 to 40 below, and the mixture was dispersed in a sand mill for about 30 hours under water cooling. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to obtain aqueous dispersions 1d to 29d.

<Comparative Examples 1d to 6d: Preparation of Aqueous Dispersions 30d to 35d>
Glass beads with a diameter of 0.2 mm were added to a mixture of each component shown in Table 41 below, and the mixture was dispersed in a sand mill for about 30 hours under water cooling. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to obtain aqueous dispersions 30d to 35d.

The numerical values of each component in Tables 37 to 41 represent parts by mass. The abbreviations in Tables 37 to 41 represent the following:
DB360: C.I. Disperse Blue 360
DB366: C.I. Disperse Blue 366
DB341: C.I. Disperse Blue 341
TS-2000: Polyoxyethylene styryl phenyl ether dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
SM-57: Polyoxyethylene styryl phenyl ether sulfate dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
Labellin W-40: Creosote oil sodium sulfonate formalin condensate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Labelin FD-40: sodium naphthalenesulfonate formalin condensate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Labelin MN-40: Sodium methylnaphthalenesulfonate formalin condensate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Demol SC-30: Sodium meta-cresol sulfonate formalin condensate (manufactured by Kao Corporation)
Morwet D425: Sodium alkylnaphthalenesulfonate formalin condensate (manufactured by Lion Specialty Chemicals Co., Ltd.)
Zetasperse 3100: Polymer resin dispersant (Evonik Japan Co., Ltd.)
BYK-190: Polymer resin dispersant (manufactured by BYK Japan Co., Ltd.)
BYK-2015: Polymer resin dispersant (manufactured by BYK Japan Co., Ltd.)
TEGODISPER 755W: Polymer resin dispersant (manufactured by Evonik Japan Co., Ltd.)
Solsperse 46000: Polymer resin dispersant (manufactured by Lubrizol Japan, Ltd.)
Solsperse J400: Polymer resin dispersant (manufactured by Lubrizol Japan, Ltd.)
TS-1500: Polyoxyethylene styryl phenyl ether dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
SM-210: Polyoxyethylene styryl phenyl ether sulfate dispersant (manufactured by Toho Chemical Industry Co., Ltd.)
Nikkol BPS-30: ethylene oxide adduct of phytosterol (manufactured by Nikko Chemicals Co., Ltd.)
Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza)
Surfynol 104PG50: Surfynol 104 (acetylene glycol surfactant, manufactured by Air Products Japan Co., Ltd.) diluted with propylene glycol to a concentration of 50%.

<Examples 30d to 58d: Preparation of Inks 1d to 29d>
The aqueous dispersions 1d to 29d obtained in Examples 1d to 29d were mixed with the components shown in Tables 42 to 45 below, stirred for 30 minutes, and then filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to prepare inks 1d to 29d, respectively.

Comparative Examples 7d to 12d: Preparation of Inks 30d to 35d
The aqueous dispersions 30d to 35d obtained in Comparative Examples 1d to 6d were mixed with the components shown in Table 46 below, stirred for 30 minutes, and then filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to prepare inks 30d to 35d, respectively.

The numerical values of each component in Tables 42 to 46 represent parts by mass. The abbreviations in Tables 42 to 46 represent the following:
BYK-348: Polyether-modified polydimethylsiloxane (manufactured by BYK Japan Co., Ltd.)
TEA-80: Triethanolamine (manufactured by Oxalis Chemicals Co., Ltd.)
Proxel GXL: Antiseptic and antifungal agent (manufactured by Lonza)

<Examples 59d to 65d and Comparative Example 13d: Preparation of aqueous dispersions 36d to 43d>
Glass beads with a diameter of 0.2 mm were added to a mixture of each component shown in Table 47 below, and the mixture was dispersed in a sand mill for about 30 hours under water cooling. The resulting liquid was filtered through a glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to obtain aqueous dispersions 36d to 43d.

The numerical values of each component in Table 47 represent parts by mass. The abbreviations in Table 47 have the same meanings as in Tables 37 to 41.

<Preparation of Examples 66d to 72d and Comparative Examples 14d to 15d: Inks 36d to 44d>
The aqueous dispersions 30d, 36d to 43d obtained in Comparative Example 1d, Examples 59d to 65d, and Comparative Example 13d were mixed with the components shown in Table 48 below, stirred for 30 minutes, and then filtered through glass fiber filter paper GC-50 (manufactured by Advantec Corporation) to prepare inks 36d to 44d, respectively.

The numerical values of each component in Table 48 represent parts by mass. The abbreviations in Table 48 have the same meanings as in Tables 42 to 46.

<Evaluation>
The aqueous dispersions 1d to 43d and inks 1d to 44d prepared as described above were used to carry out the following evaluation tests. The results are shown in Tables 37 to 48.

[Particle size change test]
The median diameter (D50, number average particle diameter) of the colorant in each aqueous dispersion or ink stored at 60° C. for 5 days was measured using a MICRO TRAC UPA EX150 (manufactured by Microtrac Corporation) and evaluated according to the following criteria: A or B indicates good storage stability, and C or D indicates poor storage stability.
-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

[Sedimentation test]
The sedimentation rate was calculated according to the following formula using the absorbance Abs ₀ at the maximum absorption wavelength (λmax) near 580 nm measured when the ink was prepared, and the absorbance Abs ₁ at the maximum absorption wavelength (λmax) near 580 nm measured by taking an aliquot of the supernatant of the ink stored at 60° C. for 5 days. The absorbance was measured using an ultraviolet-visible spectrophotometer (UV-2550, manufactured by Shimadzu Corporation) after diluting the ink 2000 times with ion-exchanged water.
Sedimentation rate (%)={(Abs ₀ −Abs ₁ )/Abs ₀ }×100
The calculated sedimentation rate was evaluated according to the following criteria: A or B indicates good storage stability, and C indicates poor storage stability.
-Evaluation criteria-
A: Sedimentation rate is less than 5%. B: Sedimentation rate is 5% or more and less than 15%. C: Sedimentation rate is 15% or more.

[Redispersibility test]
25 μL of each aqueous dispersion or ink was dropped onto a glass petri dish and dried for 1 hour in a thermostatic chamber at 60° C. 10 mL of ion-exchanged water was dropped onto the resulting dried product at room temperature, and the product was visually observed to see whether it redispersed or not, and evaluated according to the following four-level criteria. The more the ink redisperses, the easier it is to eliminate clogging after drying, and therefore the better it is. A, B, or C indicates good redispersibility, and D indicates poor redispersibility.
-Evaluation criteria-
A: No residue was left and the entire product was redispersed.
B: A small amount of residue remains, but most has been redispersed.
C: A large amount of residue remains, but is somewhat redispersed.
D: Not redispersed at all.

[Filterability test]
The ink stored at 60°C for 5 days was filtered through a filter with a pore size of 0.8 µm (DISMIC-25CS, manufactured by ADVANTEC Corporation). The amount of filtrate until the filter became clogged and filtration became impossible was measured and evaluated according to the following four-level scale. The ink with a larger amount of filtrate is superior in terms of the number of coarse particles. A or B indicates good filterability, and C indicates poor filterability.
-Evaluation criteria-
A: Filtration amount is 10 g or more B: Filtration amount is 7.5 g or more and less than 10 g C: Filtration amount is less than 7.5 g

As is clear from the results in Tables 37 to 48 above, the aqueous dispersions of Examples 1d to 29d and 59d to 65d, and the inks of Examples 30d to 58d and 66d to 72d prepared using them, all had excellent storage stability, with few coarse particles, and good sedimentation and filterability, as the particle size did not increase significantly during high-temperature storage. On the other hand, the aqueous dispersions of Comparative Examples 1d to 6d and 13d, and the inks of Comparative Examples 7d to 12d and 14d to 15d prepared using them, had inferior storage stability compared to the Examples.

Furthermore, the evaluation results of the aqueous dispersions of Examples 1d to 7d, 24d to 29d, and 59d to 65d, and the inks prepared using them of Examples 30d to 36d, 53d to 58d, and 66d to 72d, showed that redispersibility was improved by using a polyoxyethylene arylphenyl ether sulfate-based dispersant as a dispersant.

Claims (11)

(A) any one of the dyes C.I. Disperse Blue 359, C.I. Disperse Yellow 54, C.I. Solvent Orange 60, and C.I. Disperse Blue 360; (B) a dye derivative which is a compound represented by any one of the following formulas (2a), (2b), (2c-1), (2c-2), (2d-1) to (2d-3); and water;
The combination of the dye (A) and the dye derivative (B) is any one of the following combinations (a) to (d):
(a) A combination of C.I. Disperse Blue 359 and a compound represented by the following formula (2a):
(b) A combination of C.I. Disperse Yellow 54 and a compound represented by the following formula (2b):
(c) A combination of C.I. Solvent Orange 60 and at least one compound selected from the compounds represented by the following formula (2c-1) and the compounds represented by the following formula (2c-2):
(d) A combination of C.I. Disperse Blue 360 and at least one compound selected from the group consisting of a compound represented by the following formula (2d-1), a compound represented by the following formula (2d-2), and a compound represented by the following formula (2d-3):
Either
The color dispersion liquid has a content of the dye derivative (B) of 0.1 to 5 parts by mass when the total content of the dye (A) and the dye derivative (B) is 100 parts by mass.

(In formula (2a), R ^5a and R ^6a each independently represent an alkyl group having 1 to 6 carbon atoms which may have a substituent. R ^7a and R ^8a each independently represent a hydrogen atom or a halogen atom.)

(In formula (2b), A ^b represents a carbon atom or a nitrogen atom. n represents a value of 0 to 1. R ^3b and R ^4b each independently represent an aliphatic group which may have a substituent. R ^3b and R ^4b may be bonded to each other to form a monocyclic or condensed ring which may have a substituent. R ^5b represents an aliphatic group which may have a substituent. R ^3b , R ^4b and R ^5b may be bonded to each other to form a condensed ring which may have a substituent. R ^6b and R ^7b each independently represent a hydrogen atom, a hydroxyl group or a bromine atom. R ^8b and R ^9b each independently represent an aliphatic group which may have a substituent. R ^8b and R ^9b may be bonded to each other to form a monocyclic or condensed ring which may have a substituent. However, combinations of n, A ^b and R ^3b to R ^9b that result in a compound represented by formula (1b) are excluded.)

(In formula (2c-1), R ^11c to R ^16c each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, a halogen atom, a group represented by -NHR ^17c , or a group represented by -OR ^18c . R ^17c and R ^18c each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.)

(In formula (2c-2), R ^19c to R ^23c each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, a halogen atom, or a group represented by —OR ^24c . R ^24c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.)

(In formula (2d-1), R ^1d and R ^2d each independently represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms which may have a substituent, or a cyano group, except for the case where R ^1d and R ^2d simultaneously represent a hydrogen atom. R ^3d and R ^4d each independently represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms which may have a substituent, or a halogen atom.)

(In formula (2d-2), R ^5d and R ^6d each independently represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms which may have a substituent.)

(In formula (2d-3), R ^7d represents a methoxy group or a hydrogen atom. R ^8d represents a halogen atom or a group represented by -NHCOCH _3. ^{R 9d} and R ^10d each represent an alkyl group having 1 to 2 carbon atoms which may have a substituent, or a group represented by -C ₂ H ₄ OCOC ₂ H _5. ) The color dispersion according to claim 1, wherein the content of the (B) dye derivative is 0.5 to 5 parts by mass when the total content of the (A) dye and the (B) dye derivative is 100 parts by mass. The color dispersion according to any one of claims 1 to 2 , further comprising a dispersing agent. 4. The color dispersion of claim 3 , wherein the dispersant comprises a formalin condensate of an aromatic sulfonic acid or a salt thereof. 5. The color dispersion according to claim 4 , wherein the formalin condensate of an aromatic sulfonic acid or a salt thereof is a formalin condensate of sodium naphthalene sulfonate or a salt thereof. 5. The colored dispersion according to claim 4 , wherein the formalin condensate of an aromatic sulfonic acid or a salt thereof is a formalin condensate of a creosote oil sulfonic acid or a salt thereof. The color dispersion of any one of claims 3 to 6 , wherein the dispersing agent comprises a phytosterol compound. 4. The color dispersion according to claim 3 , wherein the dispersant comprises at least one selected from polyoxyethylene aryl phenyl ether-based dispersants and polyoxyethylene aryl phenyl ether sulfate-based dispersants. A recording medium having the colored dispersion liquid according to any one of claims 1 to 8 adhered thereto. The recording medium according to claim 9 , which is made of hydrophobic fibers. A printing step of depositing droplets of the color dispersion liquid according to any one of claims 1 to 8 onto an intermediate recording medium to obtain a recorded image;
a transfer step of contacting a hydrophobic fiber with a surface of the intermediate recording medium to which the color dispersion liquid has been applied and heat-treating the hydrophobic fiber to transfer the recorded image to the hydrophobic fiber;
A method for printing hydrophobic fibers comprising the steps of: