JP2001288381A - Coloring composition, ink for inkjet and inkjet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition not exhibiting a paper dependency, excellent in color development, color tons handling, smell, safety, water resis tance, light fastness, etc., enabling the high recording concentration and high picture quality, and suitable for an aqueous ink for writing, an aqueous printing ink, an information-recording ink, etc. SOLUTION: This coloring composition contains an oil soluble dyestuff of general formula I, e.g. a compound of (D-4). The form of the oil soluble dyestuff dispersed in an aqueous medium, the form containing the dyestuff dispersion obtained by dispersing the oil soluble dyestuff dissolved in a high boiling organic solvent having >=150 deg.C boiling point and 3-12 specific inductive capacity at 25 deg.C in the aqueous medium an the form of a colored fine particle dispersion obtained by dispersing the colored fine particles containing the oil soluble dyestuff and an oil soluble polymer, are preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring composition suitable for a water-based ink for writing, a water-based printing ink, an ink for information recording, etc., and a thermal, piezoelectric, electric or acoustic ink jet containing the coloring composition. The present invention relates to an inkjet ink suitable for a system and an inkjet recording method using the same.

[0002]

2. Description of the Related Art In recent years, with the spread of computers, ink jet printers have been widely used not only in offices but also at home for printing on paper, film, cloth and the like. As ink-jet inks, oil-based inks, water-based inks, and solid inks are known. Among these, water-based inks are advantageous in terms of ease of production, handling, odor, safety, etc. Ink is the mainstream.

The use of a water-soluble dye in the aqueous ink has the advantages that the ink is easy to manufacture, has excellent storage stability, has good color tone, and has high color density. However, on the other hand, the water-soluble dye has poor water resistance, and when printed on so-called plain paper, causes bleeding (bleeding), thereby causing a problem that the printing quality is remarkably deteriorated and the light resistance is poor.

Therefore, aqueous inks using pigments and disperse dyes for the purpose of solving the above-mentioned problems have been disclosed in, for example, JP-A-56-1981.
157468, JP-A-4-18468, 10-1
Nos. 10126, 10-195355, and the like. However, in the case of these water-based inks, the water resistance is improved to some extent, but is not sufficient, and the storage stability of the dispersion of the pigment or the disperse dye in the water-based ink is lacking, causing clogging at the ink ejection port. easy,
There are problems such as. In addition, these aqueous inks generally have insufficient hue and have a problem in color reproducibility based on insufficient color tone.

On the other hand, JP-A-58-45272, JP-A-6-340835, 7-268254, and 7-2
Nos. 68257 and 7-268260 propose a method of including a dye in urethane or polyester dispersion particles. However, in these cases, the color reproducibility based on insufficient color tone is not sufficient, and the dispersion stability and water resistance of the dye-containing polymer dispersion when the dye is included at a desired concentration are not necessarily sufficient. There is.

[0006]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems in the prior art, has no paper dependence, has excellent color developability and color tone when printed on arbitrarily selected paper, and has excellent handleability and odor. Excellent in safety, water resistance, light resistance, etc., enabling high recording density and high image quality, aqueous ink for writing, aqueous printing ink,
A coloring composition suitable for an information recording ink or the like, containing the coloring composition, and suitable for a thermal, piezoelectric, electric field or acoustic ink jet system. When printing or the like is performed using a nozzle or the like, an There is no clogging, no dependence on paper, and color development when printing on arbitrarily selected paper.
Excellent color tone, and water-resistant, light-fast inkjet ink, and, using the inkjet ink,
An object of the present invention is to provide an ink jet recording method capable of high quality recording.

[0007]

Means for solving the above problems are as follows. That is, <1> a colored composition containing an oil-soluble dye represented by the following formula (I). Formula (I)

[0008]

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In the above formula (I), Q represents an atomic group necessary for the compound represented by the above formula (I) to have an absorption in a visible region and / or a near infrared region. R ₁ is an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group,
Carbamoyl groups, alkyl and arylsulfonyl groups,
Represents a sulfamoyl group or a phosphinyl group. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R ₂ and R ₃ may combine with each other to form a ring structure.

<2> The colored composition according to <1>, wherein the oil-soluble dye is dispersed in an aqueous medium. <3> A dye dispersion obtained by dispersing, in an aqueous medium, an oil-soluble dye dissolved in a high-boiling organic solvent having a boiling point of 150 ° C. or higher and a relative dielectric constant at 25 ° C. of 3 to 12 in the aqueous medium. 2>. <4> The colored composition according to <2>, further including a colored fine particle dispersion in which colored fine particles containing an oil-soluble dye and an oil-soluble polymer are dispersed in an aqueous medium. <5> The colored composition according to <4>, wherein the colored fine particle dispersion contains a high-boiling organic solvent. <6> The colored composition according to <4> or <5>, wherein the colored fine particles have an oil-soluble dye dispersed in an oil-soluble polymer. <7> The above <1> to <6> used in the ink composition
The coloring composition according to any one of <1> to <3>. <8> An inkjet ink comprising the coloring composition according to any one of <1> to <7>. <9> An ink jet recording method characterized by performing recording using the ink for ink jet described in <8>.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the coloring composition, ink jet ink and ink jet recording method of the present invention will be described.

(Coloring composition) First, the coloring composition of the present invention contains an oil-soluble dye, and the oil-soluble dye is dispersed in an aqueous medium. The aqueous medium only needs to contain at least water, and specifically, water, or a mixture of water and a water-miscible organic solvent, if necessary, a surfactant, an anti-drying agent ( Suitable additives include additives such as a wetting agent, a stabilizer, and a preservative.

<Oil-soluble dye> The oil-soluble dye is a compound represented by the following formula (I) and is an oil-soluble azomethine dye. Formula (I)

[0014]

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In the above formula (I), R ₁ represents an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an alkyl and arylsulfonyl group, a sulfamoyl group, or a phosphinyl group.

Among the above acyl groups, a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms,
A substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms (e.g., acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl) is preferred.

Among the above aryloxycarbonyl groups, a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms (for example, phenoxycarbonyl group, o-
Chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl).

Among the above alkoxycarbonyl groups, a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, n-octadecyloxycarbonyl group) is preferable.

Among the carbamoyl groups, those having 1 to 1 carbon atoms
30 substituted or unsubstituted carbamoyl groups (eg, carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group)
Is preferred.

Among the alkyl and arylsulfonyl groups, substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms (for example, methylsulfonyl group, ethylsulfonyl group, Phenylsulfonyl group and p-methylphenylsulfonyl group) are preferred.

Among the above sulfamoyl groups, those having 0 carbon atoms
~ 30 substituted or unsubstituted sulfamoyl groups (e.g.,
N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N '-Phenylcarbamoyl) sulfamoyl group) is preferred.

Among the phosphinyl groups, those having 2 to 2 carbon atoms
Preferred are 30 substituted or unsubstituted phosphinyl groups (eg, phosphinyl group, dioctyloxyphosphinyl group, diethoxyphosphinyl group).

The group represented by R ₁ may further have a substituent. In this case, the following substituents are preferable. For example, a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group,
Cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (anilino group ), An acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl and arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, Sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group,
Examples include a carbamoyl group, an aryl and heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

As the halogen atom, for example, a chlorine atom, a bromine atom and an iodine atom are preferable.

Examples of the alkyl group include a linear, branched or cyclic substituted or unsubstituted alkyl group, and in addition to the alkyl group, a cycloalkyl group, a bicycloalkyl group, a tricyclo structure having a large number of ring structures, and the like. included.

Among the above alkyl groups, those having 1 to 30 carbon atoms
(E.g., methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, and 2-ethylhexyl) are preferred. . Among the above cycloalkyl groups, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms (for example, cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group)
Is preferred. Among the bicycloalkyl groups, a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms (for example, bicyclo [1, 2 ,
2] heptane-2-yl and bicyclo [2,2,2] octan-3-yl group) are preferred. An alkyl group in a substituent described below (for example, an alkyl group of an alkylthio group) also represents an alkyl group having such a concept.

Examples of the alkenyl group include a linear, branched or cyclic substituted or unsubstituted alkenyl group, and in addition to the alkenyl group, include a cycloalkenyl group and a bicycloalkenyl group.

Among the alkenyl groups, those having 2 to 3 carbon atoms
0 substituted or unsubstituted alkenyl group (eg, vinyl group, allyl group, prenyl group, geranyl group, oleyl group)
Is preferred. Among the cycloalkenyl groups, a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopentene-1) −
Yl, 2-cyclohexen-1-yl group) is preferred.
Among the bicycloalkenyl groups, a substituted or unsubstituted bicycloalkenyl group is mentioned, and a hydrogen atom of a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, one hydrogen atom of a bicycloalkene having one double bond is removed. Monovalent groups (for example, bicyclo [2,2,1] hept-
2-en-1-yl group and bicyclo [2,2,2] oct-2-en-4-yl group) are preferred.

Among the alkynyl groups, those having 2 to 3 carbon atoms
A substituted or unsubstituted alkynyl group of 0 is preferable, and for example, an ethynyl group, a propargyl group, a trimethylsilylethynyl group and the like are preferable.

Among the above aryl groups, those having 6 to 30 carbon atoms
Or a substituted or unsubstituted aryl group, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, and o-hexadecanoylaminophenyl.

Among the above heterocyclic groups, 5 or 6 members
A monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound having 1 to 3 carbon atoms is preferable, and a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms is preferable. Are more preferable, for example, a 2-furyl group, 2
-Thienyl, 2-pyrimidinyl, 2-benzothiazolyl and the like are particularly preferred.

Among the above alkoxy groups, those having 1 to 3 carbon atoms
A substituted or unsubstituted alkoxy group of 0 is preferable, for example, a methoxy group, an ethoxy group, an isopropoxy group, a t-
Butoxy, n-octyloxy, 2-methoxyethoxy and the like are more preferred.

Among the above aryloxy groups, those having 6 carbon atoms
~ 30 substituted or unsubstituted aryloxy groups are preferred, for example, phenoxy group, 2-methylphenoxy group,
4-t-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group, and the like are more preferable.

Among the above silyloxy groups, those having 3 to 3 carbon atoms
20 silyloxy groups are preferred, for example, a trimethylsilyloxy group, a t-butyldimethylsilyloxy group,
And the like are more preferable.

Among the above heterocyclic oxy groups, those having 2 carbon atoms
A substituted or unsubstituted heterocyclic oxy group of up to 30 is preferable, and for example, a 1-phenyltetrazole-5-oxy group, a 2-tetrahydropyranyloxy group and the like are more preferable.

Among the above acyloxy groups, a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, and the like are preferable. , Formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy, and the like.

Among the carbamoyloxy groups, a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms is preferable. For example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group Groups, N, N-di-n-octylaminocarbonyloxy groups, Nn-octylcarbamoyloxy groups, and the like are more preferred.

Among the above alkoxycarbonyloxy groups, a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms is preferable, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, t-butoxycarbonyloxy group, n-octyl. A carbonyloxy group is more preferred.

Of the above aryloxycarbonyloxy groups, a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms is preferable. For example, a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, a p-n- A hexadecyloxyphenoxycarbonyloxy group is more preferred.

Among the above amino groups, in addition to the amino group,
A substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms,
Examples thereof include a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, and a diphenylamino group.

Among the acylamino groups, a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, and the like are preferable. , Formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group,
A 3,4,5-tri-n-octyloxyphenylcarbonylamino group and the like are more preferred.

Among the above aminocarbonylamino groups,
A substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms is preferable. For example, a carbamoylamino group, N,
More preferred are an N-dimethylaminocarbonylamino group, an N, N-diethylaminocarbonylamino group, a morpholinocarbonylamino group, and the like.

Among the above alkoxycarbonylamino groups, a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms is preferred, for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyl. An oxycarbonylamino group, an N-methyl-methoxycarbonylamino group, and the like are more preferred.

Among the above-mentioned aryloxycarbonylamino groups, a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms is preferable, for example, phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn- An octyloxyphenoxycarbonylamino group is more preferred.

Among the above sulfamoylamino groups, a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms is preferable. For example, a sulfamoylamino group, N,
An N-dimethylaminosulfonylamino group, an Nn-octylaminosulfonylamino group, and the like are more preferable.

Among the above-mentioned alkyl and arylsulfonylamino groups, a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms are preferable.
For example, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-
A trichlorophenylsulfonylamino group, a p-methylphenylsulfonylamino group, and the like are more preferable.

Among the above alkylthio groups, those having 1 to 1 carbon atoms
30 substituted or unsubstituted alkylthio groups are preferable, and for example, a methylthio group, an ethylthio group, an n-hexadecylthio group, and the like are more preferable.

The arylthio group has 6 to 6 carbon atoms.
Preferred are 30 substituted or unsubstituted arylthio groups such as phenylthio, p-chlorophenylthio, m
-Methoxyphenylthio group, and the like are more preferred.

Among the above heterocyclic thio groups, those having 2 to 2 carbon atoms
30 substituted or unsubstituted heterocyclic thio groups are preferred, for example, a 2-benzothiazolylthio group, a 1-phenyltetrazol-5-ylthio group, and the like are more preferred.

Among the sulfamoyl groups, those having 0 carbon atoms
~ 30 substituted or unsubstituted sulfamoyl groups are preferred, for example, N-ethylsulfamoyl group, N- (3-
Dodecyloxypropyl) sulfamoyl group, N, N-
Dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N'-
Phenylcarbamoyl) sulfamoyl, and the like are more preferred.

Among the above-mentioned alkyl and arylsulfinyl groups, a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms are preferable. An ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group, and the like are more preferable.

Among the above-mentioned alkyl and arylsulfonyl groups, a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, and the like are preferable. Ethylsulfonyl group, phenylsulfonyl group, p-
A methylphenylsulfonyl group is more preferred.

Among the acyl groups, a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms,
A substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms is preferable, for example, an acetyl group, a pivaloyl group, a 2-chloroacetyl group, a stearoyl group, a benzoyl group, a pn-octyloxyphenylcarbonyl group,
And the like are more preferable.

Among the above-mentioned aryloxycarbonyl groups, a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms is preferable. For example, a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, -T-butylphenoxycarbonyl group and the like are more preferable.

Among the above alkoxycarbonyl groups, a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms is preferable. Examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group and an n-octadecyloxycarbonyl group. Is preferred.

Among the carbamoyl groups, those having 1 to 1 carbon atoms
Preferred are 30 substituted or unsubstituted carbamoyl groups, for example, carbamoyl group, N-methylcarbamoyl group, N,
N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like are preferred.

Among the above-mentioned aryl and heterocyclic azo groups, a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms and a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms are preferable. Group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group, and the like are more preferable.

Among the imide groups, N-succinimide, N-phthalimide and the like are preferable. Among the phosphino groups, a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms is preferable, for example, a dimethylphosphino group,
Diphenylphosphino groups, methylphenoxyphosphino groups, and the like are more preferred. Among the phosphinyl groups, a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms is preferable, and for example, a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, and the like are preferable.

Among the above phosphinyloxy groups, a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms is preferable, for example, diphenoxyphosphinyloxy group, dioctyloxyphosphinyloxy group and the like. Is more preferred. Among the phosphinylamino groups, a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms is preferable, for example, a dimethoxyphosphinylamino group,
A dimethylaminophosphinylamino group is more preferred.

Among the above silyl groups, a substituted or unsubstituted silyl group having 3 to 30 carbon atoms is preferable, and for example, a trimethylsilyl group, a t-butyldimethylsilyl group, a phenyldimethylsilyl group and the like are more preferable.

Among the above R ₁ , an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group and a carbamoyl group are preferred, and an aryloxycarbonyl group and an alkoxycarbonyl group are more preferred.

In the above formula (I), R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Preferable carbon numbers and specific examples of the alkyl group, the aryl group, or the heterocyclic group represented by R ₂ or R ₃ are the same as the groups represented by R ₁ . R ₂ and R ₃ may combine with each other to form a ring structure, and the ring formed by combining R ₂ and R ₃ is preferably the following.

[0063]

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Among the above R ₂ and R ₃ , those having 1 to 30 carbon atoms
Is more preferred.

In the above formula (I), Q represents an atomic group necessary for the compound represented by the above formula (I) to have an absorption in a visible region and / or a near infrared region. Is the following (C
Groups represented by p-1) to (Cp-27) are preferred.
In addition, the group represented by the following (Cp-1) to (Cp-27) is bonded to a part other than Q in the formula (I) at the position of * mark.

[0066]

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[0067]

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[0068]

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Here, (Cp-1) to (Cp-27) will be described.

In (Cp-1), R₅₁Is an alkyl
Group, aryl group, heterocyclic group, or alkoxy group
You. The R₅₁Among them, t-butyl group, 1-ethylcyclyl
L-propyl group, 1-methylcyclopropyl group, 1-ben
Zylcyclopropyl group, substituted or unsubstituted phenyl
Group, substituted or unsubstituted indolinin-1-yl group,
Or a substituted or unsubstituted indol-3-yl group is preferred.
Good. In (Cp-1), R₅₂Is carbamoyl
Represents a group or a cyano group. The R ₅₂Among them, N-Ally
A rucarbamoyl group or a cyano group is preferred.

In (Cp-2), R₅₃Is an aryl
Represents a group or a heterocyclic group. The R₅₃Among the substitution or
Unsubstituted phenyl groups and substituted or unsubstituted heterocyclic groups are preferred.
Preferably, thiazol-2-yl, benzothiazol-2
-Yl, oxazol-2-yl, benzoxazole
-2-yl, 1,2,4-oxadiazole-3 (or
5) -yl, 1,3,4-oxadiazole-2 (or
5) -yl, 1,2,4-thiadiazole-3 (or
5) -yl, 1,3,4-thiadiazole-2 (or
5) -yl, pyrazol-3-yl, indazole-3
-Yl, 1,2,4-triazol-3-yl, 2-pi
Lysyl, 2-pyrimidinyl, 2-pyrazinyl, quinazoli
2--2-yl or quinazolin-4-yl is more preferred.
No. In (Cp-2), R₅₂Is a carbamoyl group or
Represents a cyano group. The R ₅₂Of these, cyano groups are preferred.
New

In (Cp-3), R ₆₁ represents an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aminocarbonylamino group, or an alkoxy group. Represents a carbonylamino group. Among the R _61, an alkyl group, an acylamino group, an amino group, an aminocarbonyl amino group, or alkoxy are preferred carbonylamino group, an acylamino group or an N- arylamino group, more preferable. In (Cp-3), R ₆₂ represents an alkyl group, an aryl group, or a heterocyclic group. The R
Among ₆₂ , an aryl group or a heterocyclic group is preferable, and an aryl group is more preferable.

In (Cp-4), R ₆₃ and R ₆₄ are
A hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an amino group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an aminocarbonylamino group, or Represents an alkoxycarbonylamino group. Among the above R ₆₃ , an alkyl group,
An aryl group, an alkoxy group, or an aryloxy group is preferable, and a methyl group, a t-butyl group, or a substituted or unsubstituted phenyl group is more preferable. Among the above R ₆₄ , an alkyl group or an aryl group is preferable.

In (Cp-5) and (Cp-6),
R ₆₃ represents a group having the same meaning as R ₆₃ . Among the above R ₆₃ , an alkyl group, an aryl group, an alkoxy group, or an aryloxy group is preferable. (Cp-5) and (Cp-
In 6), R ₆₅ , R ₆₆ and R ₆₇ each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an alkyl or arylsulfonylamino group, an amino group, an alkylthio group, an arylthio group, Represents an aryloxy group, an aminocarbonylamino group, an alkoxycarbonylamino group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. R ₆₅ , R
Among them, ₆₆ and R ₆₇ are preferably a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group.

In (Cp-7), R ₆₈ and R ₆₉ each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
Represents an acylamino group, an alkyl and arylsulfonylamino group, an amino group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an aminocarbonylamino group, an alkoxycarbonylamino group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. Among R ₆₈ and R ₆₉ , a hydrogen atom, an alkyl group, or an aryl group is preferable.

(Cp-8), (Cp-9), (Cp-1)
In (0) and (Cp-11), R ₇₀ represents an alkyl group, an aryl group, or a heterocyclic group. Among the above R ₇₀ , an alkyl group or an aryl group is preferable. (Cp-
8), (Cp-9) and (Cp-10)
₇₁ is a halogen atom, alkyl group, aryl group, heterocyclic group, silyl group, acylamino group, alkyl and arylsulfonylamino group, amino group, aminocarbonylamino group, alkylthio group, arylthio group, alkoxy group, alkoxycarbonylamino group Represents Among the R _71, a halogen atom, an alkyl group, or an acylamino group. In (Cp-11), R ₇₂ represents a hydrogen atom or an alkyl group. Among the R _72, a hydrogen atom, a methyl group, or ethyl group is preferred. (Cp-
8), (Cp-9), (Cp-10) and (Cp-1)
In 1), a represents an integer of 0 to 3, b represents an integer of 0 to 2, and c represents an integer of 0 to 4. Among the above a, 1 or 2 is preferable, among b, 1 or 2 is preferable, and among c, an integer of 0 to 2 is preferable. a, b,
Or, when c is plural, plural R ₇₁ may be the same or different. In (Cp-11),
R ₇₃ represents a hydrogen atom or an alkyl group. Of the above R ₇₃ , a hydrogen atom, a methyl group, or an ethyl group is preferable.

In (Cp-12), R ₇₄ represents a carbamoyl group, an alkoxycarbonyl group, a cyano group, a sulfamoyl group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, or an alkyl and arylsulfonylamino group. Among the above R ₇₄ , a carbamoyl group, a sulfamoyl group, or an acylamino group is preferable. In (Cp-12), R ₇₅ represents
Halogen atom, alkyl group, aryl group, heterocyclic group,
Represents an acylamino group, an alkyl or arylsulfonylamino group, an amino group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an aminocarbonylamino group, or an alkoxycarbonylamino group. Among the R _75, an acylamino group, an alkylsulfonylamino group, aminocarbonylamino group, or an alkoxycarbonyl amino group. (Cp-1
In 2), d represents an integer of 0 to 4. Of the above d, 0 or 1 is preferable. When d is plural, plural R
₇₅ may be the same or different from each other.

In (Cp-13), R ₇₅ and d are
Represents the same meaning as above. Among the above R ₇₅ , a halogen atom, an alkyl group or an aryl group is preferable, and among the above d, an integer of 0 to 2 is preferable. In (Cp-13), R ₇₈ and R ₇₉ represent a group having the same meaning as R ₇₅ described above. Among R ₇₈ and R ₇₉ , a halogen atom, an alkyl group, or an aryl group is preferable. In (Cp-13), R ₇₆ and R ₇₇ represent a cyano group, a sulfamoyl group,
Represents an alkyl and aryl sulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. The R
Among ₇₆ and R _77, a cyano group is preferable.

In (Cp-14), R ₇₅ and d have the same meanings as described above. Among the R _75, a halogen atom, an alkyl group, or an aryl group is preferable, an integer of 0 to 2 is preferred among the d. In (Cp-14), R ₈₀ and R ₈₁ represent a cyano group, a sulfamoyl group, an alkyl and aryl sulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. Among R ₈₀ and R ₈₁ , a cyano group is preferable.

In (Cp-15), R ₈₂ , R ₈₃ and R ₈₄ each represent a hydrogen atom, an alkyl group, an aryl group,
Heterocyclic group, acylamino group, alkyl and arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxy group, aryloxy group, aminocarbonylamino group, or alkoxycarbonylamino group, acyl group, alkoxycarbonyl group, or carbamoyl Represents a group.

In (Cp-16), R ₈₅ and R
₈₆ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an alkyl and arylsulfonylamino group, an amino group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an aminocarbonylamino group, an alkoxy group, respectively. Represents a carbonylamino group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. Among the above R ₈₅ and R ₈₆ , a hydrogen atom, an alkyl group,
An aryl group, a heterocyclic group, an acylamino group, an alkylsulfonylamino group, and an arylsulfonylamino group are preferred.

(Cp-17), (Cp-18) and (Cp-18)
In p-19), R ₈₇ and R ₈₈ represent a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a sulfamoyl group, an alkanesulfonyl group, an arenesulfonyl group, or a nitro group. Among R ₈₇ , a carbamoyl group, an alkoxycarbonyl group, or a cyano group is preferable, and a cyano group is more preferable. Among the R _88, a carbamoyl group, an alkoxycarbonyl group, a cyano group, or an alkyl or arylsulfonyl group is preferable, an alkoxycarbonyl group, more preferably. (Cp-17), (Cp-18) and (Cp-18)
In p-19), R ₈₉ and R ₉₀ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₈₉
And R ₉₀ , an alkyl group or an aryl group is preferable, and an aryl group is more preferable.

(Cp-20) to (Cp-25)
And R₉₁And R₉₂Is an alkyl group, an aryl group, a hetero ring
Group, carbamoyl group, alkoxycarbonyl group, aryl
Ruoxycarbonyl group, cyano group, sulfamoyl group,
Alkane sulfonyl group, arene sulfonyl group, or
Represents a toro group. The R₉₁Among them, aryl group, hetero group
Ring group, carbamoyl group, alkoxycarbonyl group, shea
Nono groups are preferred. The R ₉₂Among them, carbamoyl group,
Alkoxycarbonyl group, cyano group, sulfamoyl
Group, or alkylsulfonyl group, and arylsulfonyl group
Preferred is a thiol group. (Cp-20) to (Cp-25)
And R₉₃, R₉₄, And R₉₅Represents a hydrogen atom, an alkyl group,
Aryl group, heterocyclic group, acylamino group, aminocar
Bonylamino group, alkoxycarbonylamino group, al
Kill and arylsulfonylamino groups, halogen atoms,
Amino group, alkylthio group, arylthio group, alkoxy
Represents a silyl group or an aryloxy group. The R₉₃, R₉₄,
And R₉₅Among them, hydrogen atom, alkyl group, acylamino
Group, halogen atom, amino group, alkylthio group, or
A reelthio group is preferred.

In (Cp-26), R ₉₆ represents an amino group, an alkylthio group, an arylthio group, an alkoxy group,
Or an aryloxy group. Among the above _R96 , N-
Arylamino groups are preferred. In _{(Cp-26), R 97} , R 98, and R ₉₉ each represent a hydrogen atom, a cyano group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or carbamoyl group. Among R ₉₇ , R ₉₈ and R ₉₉ , a hydrogen atom or a cyano group is preferable.

In (Cp-27), R ₁₀₀ and R ₁₀₁
Is a hydrogen atom, a perfluoroalkyl group, a cyano group, a nitro group, a sulfamoyl group, an alkyl and arylsulfonyl group, an acyl group, an alkoxycarbonyl group,
Represents a carbamoyl group, an alkylthio group, or an arylthio group. Wherein R ₁₀₀ and R ₁₀₁ preferably a hydrogen atom, a perfluoroalkyl group, a cyano group, a nitro group, an alkyl- or arylsulfonyl group, an alkylthio group, or an arylthio group. In (Cp-27), R ₁₀₂ represents an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, an alkyl and arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. Among the R _102, an aryl group or a heterocyclic group.

R _{51 to} R ₅₃ , R _{61 to} R ₆₉ , and R _{70 to} R
The preferred carbon number and specific examples of the group represented by ₁₀₂ are the same as those described for the group represented by R ₁ . R _{51 to} R
_The groups represented by ₅₃ , R _{61 to} R ₆₉ , and R _{70 to} R ₁₀₂ may further have a substituent, and in that case, preferred substituents are the substituents of the group represented by R ₁ It is the same as what was mentioned as.

Among the groups represented by (Cp-1) to (Cp-27), (Cp-1), (Cp-2) and (Cp-
4), (Cp-10), (Cp-11), (Cp-1)
7), (Cp-20) and (Cp-21) are particularly preferred.

The total number of carbon atoms in the substituent of the oil-soluble azomethine dye represented by the formula (I) is preferably 8 to 40, and more preferably at least one having 10 to 30 diffusion-resistant groups. preferable. The oil-soluble azomethine dye represented by the formula (I) may be a bis-type, tris-type, telomer-type or polymer-type compound having two or more dye skeletons in the molecule. In this case, the range of the number of carbon atoms may be outside the above range.

The oil-soluble azomethine dye represented by the formula (I) may have an atomic group having an effect of suppressing fading in the molecule. This is described in JP-A-3-205189.

Exemplary compounds (D-1 to D-33) of the oil-soluble azomethine dye represented by the formula (I) are shown below.

[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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The method for synthesizing the oil-soluble azomethine dye of the present invention is described in JP-A-3-244593 and JP-A-4-9381.
It is described in the specification.

The colored composition of the present invention is preferably in the form of a dispersion containing colored fine particles or a dispersion of dyes.

<Colored Fine Particle Dispersion> The colored fine particle dispersion is obtained by dispersing colored fine particles containing the oil-soluble dye and the oil-soluble polymer in the aqueous medium.

The oil-soluble polymer is not particularly limited and can be appropriately selected from conventionally known ones. Examples thereof include vinyl polymers, condensation polymers (polyurethane,
Polyester, polyamide, polyurea, polycarbonate) and the like.

The oil-soluble polymer may be any of a water-insoluble type, a water-dispersible (self-emulsifying) type, and a water-soluble type. The type is preferred.

The water-dispersible polymer may be any of an ionic polymer, a nonionic dispersible group-containing polymer, and a mixed polymer thereof.

Examples of the ionic polymer include a polymer having a cationic group such as a tertiary amino group and a polymer having an anionic dissociable group such as a carboxylic acid and a sulfonic acid. Examples of the nonionic dispersible group-containing polymer include a polymer containing a nonionic dispersible group such as a polyethyleneoxy group. Among these, from the viewpoint of dispersion stability of the colored fine particles, an ionic polymer containing an anionic dissociable group, a nonionic dispersible group-containing polymer, and a mixed polymer thereof are preferable.

Examples of the monomer forming the vinyl polymer include acrylic acid esters and methacrylic acid esters (the ester group is an ester group of an alkyl group and an aryl group which may have a substituent,
Examples of the alkyl group and the aryl group include methyl, ethyl, n-butyl, sec-butyl, tert-butyl, hexyl, 2-ethylhexyl, tert-octyl, 2-chloroethyl, cyanoethyl, 2-acetoxyethyl, and tetrahydrofurfuryl. , 5-hydroxypentyl, cyclohexyl, adamantyl, norbornyl,
Benzyl, hydroxyethyl, 3-methoxybutyl, 2
-(2-methoxyethoxy) ethyl, 2,1,1,2,
Vinyl esters such as 2-tetrafluoroethyl, perfluorodecyl, phenyl, 2,4,5-trimethylphenyl, 4-chlorophenyl and the like.

Examples of the vinyl esters include:
Aliphatic carboxylic acid vinyl ester (specifically, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, etc.), aromatic carboxylic acid vinyl ester (specifically, Include vinyl benzoate, vinyl 4-methylbenzoate, vinyl salicylate, etc.), and these may have a substituent.

Examples of the other monomers forming the vinyl polymer include acrylamides, methacrylamides, olefins, and other monomers.

Examples of the acrylamides include acrylamide, N-monosubstituted acrylamide,
N, N-disubstituted acrylamide (the substituent is an alkyl group, an aryl group, a silyl group; for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
-Butyl group, tert-butyl group, tert-octyl group, cyclohexyl group, adamantyl group, norbornyl group, benzyl group, hydroxymethyl group, ethoxyethyl group, phenyl group, 2,4,5-tetramethylphenyl group, 4- A chlorophenyl group and a trimethylsilyl group, which may further have a substituent. ), And the like.

Examples of the methacrylamides include methacrylamide, N-monosubstituted methacrylamide, N, N-disubstituted methacrylamide (for example, methyl, ethyl, n- Propyl, isopropyl, n-butyl, tert-butyl, t
ert-octyl group, cyclohexyl group, adamantyl group, norbornyl group, benzyl group, hydroxymethyl group, ethoxyethyl group, phenyl group, 2,4,5-trimethylphenyl group, 4-chlorophenyl group, trimethylsilyl group, which are further substituted It may have a group. ), And the like.

Examples of the olefins include olefins (eg, ethylene, propylene, 1-pentene, vinyl chloride, vinylidene, isoprene, chloroprene, butadiene) and styrenes (eg, styrene, methyl styrene, isopropyl styrene, methoxy styrene, Acetoxystyrene, chlorostyrene), vinyl ethers (eg, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether) and the like.

Examples of the other monomers include crotonic esters, itaconic esters, maleic esters, fumaric esters, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N
-Vinyloxazolidone, N-vinylpyrrolidone, vinylidene chloride, methylenemalononitrile, vinylidene, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, dioctyl-2-methacryloyl Oxyethyl phosphate, and the like.

The monomers having a dissociable group include:
Examples of the monomer include a monomer having an anionic dissociative group and a monomer having a cationic group. Examples of the monomer having an anionic dissociable group include a carboxylic acid monomer, a sulfonic acid monomer, and a phosphoric acid monomer.

Examples of the carboxylic acid monomer include acrylic acid, methacrylic acid, maleic acid itaconic acid, fumaric acid, citraconic acid, crotonic acid, and monoalkyl itaconate (eg, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate). And monoester maleate (for example, monomethyl maleate, monoethyl maleate, monobutyl maleate), and the like.

Examples of the sulfonic acid monomer include styrene sulfonic acid, vinyl sulfonic acid, acryloyloxyalkanesulfonic acid (for example, acryloyloxyethanesulfonic acid, acryloyloxypropanesulfonic acid), and methacryloyloxyalkanesulfonic acid (for example, methacryloyl). Oxyethanesulfonic acid,
Methacryloyloxypropanesulfonic acid), acrylamidoalkanesulfonic acid (for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid), methacrylamidoalkanesulfonic acid (for example, 2-methacrylamide-)
2-methylethanesulfonic acid, 2-methacrylamide-
2-methylpropanesulfonic acid, 2-methacrylamide-2-methylbutanesulfonic acid) and the like.

Examples of the phosphoric acid monomer include vinyl phosphonic acid and methacryloyloxyethyl phosphonic acid.

Among these, acrylic acid, methacrylic acid, styrene sulfonic acid, vinyl sulfonic acid, acrylamide alkyl sulfonic acid, and methacrylamido alkyl sulfonic acid are preferred as the monomer having an anionic dissociable group. , Methacrylic acid,
Styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2-acrylamido-2-methylbutanesulfonic acid are more preferred.

Examples of the monomer having a cationic group include monomers having a tertiary amino group such as dialkylaminoethyl acrylate and dialkylaminoethyl methacrylate.

Examples of the monomer having a nonionic dispersing group include esters of polyethylene glycol monoalkyl ether and carboxylic acid monomer, esters of polyethylene glycol monoalkyl ether and sulfonic acid monomer, and polyethylene glycol monoalkyl. Esters of ether and phosphoric acid monomers, vinyl group-containing urethanes formed from polyethylene glycol monoalkyl ether and isocyanate group-containing monomers, macromonomers having a polyvinyl alcohol structure, and the like. The number of repeating ethyleneoxy units of the polyethylene glycol monoalkyl ether is preferably from 8 to 50, and more preferably from 10 to 30. The number of carbon atoms of the alkyl group of the polyethylene glycol monoalkyl ether is preferably from 1 to 20, and more preferably from 1 to 12.

Next, the condensation polymer will be described in detail. The polyurethane is basically synthesized by a polyaddition reaction using a diol compound and a diisocyanate compound as raw materials. Specific examples of the diol compound, as a non-dissociable diol, ethylene glycol,
1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 2,2, -dimethyl-1,3-propanediol,
1,4-pentanediol, 2,4-pentanediol, 3,3-dimethyl-1,2-butanediol, 2-
Ethyl-2-methyl-1,3-propanediol, 1,
6-hexanediol, 2,5-hexanediol, 2
-Methyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol, 2,4-dimethyl-
2,4-pentanediol, 2-methyl-2-propyl 1,3-propanediol, 2,5-dimethyl-2,5
-Hexanediol, 2-ethyl-1,3-hexanediol, 1,2-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol , Dipropylene glycol, tripropylene glycol, polyethylene glycol (average molecular weight = 200, 300, 400, 600, 1000, 150
0, 4000), polypropylene glycol (average molecular weight = 200, 400, 1000), polyester polyol, 4,4′-dihydroxy-diphenyl-2,2-
And propane and 4,4-dihydroxyphenylsulfone.

Examples of the diol compound having an anionic group include 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butanoic acid,
2,5,6-trimethoxy-3,4-dihydroxyhexanoic acid, 2,3-dihydroxy-4,5-dimethoxypentanoic acid, 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid, and these Examples thereof include salts, but are not particularly limited thereto.

Preferred specific examples of the diisocyanate compound include ethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate,
1,4-cyclohexane diisocyanate, 2,4-toluene diisocyanate, 1,3-xylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′- Examples include diphenylmethane diisocyanate, 3,3′-dimethylbiphenylene diisocyanate, dicyclohexylmethane diisocyanate, and methylene bis (4-cyclohexyl isocyanate).

The polyester can be easily synthesized basically by dehydration condensation of a diol compound and a dicarboxylic acid compound.

Specific examples of the dicarboxylic acid compound include oxalic acid, malonic acid, succinic acid, glutaric acid, dimethylmalonic acid, adipic acid, pimelic acid, α, α-dimethylsuccinic acid, acetonedicarboxylic acid, sebacic acid, and the like.
1,9-nonanedicarboxylic acid, fumaric acid, maleic acid,
Itaconic acid, citraconic acid, phthalic acid, isophthalic acid,
Terephthalic acid, 2-butylterephthalic acid, tetrachloroterephthalic acid, acetylenedicarboxylic acid, poly (ethylene terephthalate) dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, ω-poly (ethyleneoxy) dicarboxylic acid Acids, p-xylylenedicarboxylic acid, and the like. These compounds may be used in the form of an alkyl ester of a carboxylic acid (for example, dimethyl ester) or an acid chloride of a dicarboxylic acid when performing polycondensation with the diol compound,
It may be used in the form of an acid anhydride such as maleic anhydride, succinic anhydride, and phthalic anhydride.

Preferred examples of the dicarboxylic acid compound having a sulfonic acid group and the diol compound include sulfophthalic acids (for example, 3-sulfophthalic acid, 4-sulfophthalic acid, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, and 2-sulfophthalic acid). Terephthalic acid, etc.), sulfosuccinic acid, sulfonaphthalenecarboxylic acids (for example, 4-sulfo-
1,8-naphthalenedicarboxylic acid, 7-sulfo-1,5
-Naphthalenecarboxylic acid, etc.), 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid, and salts thereof.

As the diol compound, a compound selected from the same group as the diols described for the polyurethane is used. A typical synthesis method of the polyester is a condensation reaction of the diols with a dicarboxylic acid or a derivative thereof, but can also be obtained by condensing a hydroxycarboxylic acid (for example, 1,2-hydroxystearic acid or the like). Polyesters obtained by a method such as a ring-opening polymerization method of a cyclic ether and a lactone (see Lecture Polymerization Reaction 6, Ring-Opening Polymerization (I), written by Takeo Saegusa, 1971) are also included in the present invention. It is preferably used.

The polyamide can be obtained by polycondensation of a diamine compound and a dicarboxylic acid compound, polycondensation of an aminocarboxylic acid compound, ring-opening polymerization of lactams, and the like. Examples of the diamine compound include ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, hexamethylenediamine, octamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, piperazine, and 2,5. -Dimethylpiperazine, 4,4'-diaminophenylether, 3,3'-diaminodiphenylsulfone, xylylenediamine and the like. As the aminocarboxylic acid, glycine, alanine, phenylalanine, ω
-Aminohexanoic acid, ω-aminodecanoic acid, ω-aminoundecanoic acid, anthranilic acid and the like. Examples of the monomer used for the ring-opening polymerization include ω-caprolactam, azetidinone, and pyrrolidone. As the dicarboxylic acid compound, a compound selected from the same group as the dicarboxylic acids described in the polyester is used.

The polyurea can be obtained basically by polyaddition of a diamine compound and a diisocyanate compound, and a deammonification reaction of the diamine compound and urea. As the diamine compound as a raw material, a compound selected from the same group as the diamines described for the polyamide can be used. As the diisocyanate compound as a raw material, a compound selected from the same group as the diisocyanates described in the polyurethane can be used.

The polycarbonate can be basically obtained by reacting a diol compound with a phosgene or carbonate derivative (eg, an aromatic ester such as diphenyl carbonate). As the diol compound as a raw material, a compound belonging to the same group as the diols described in the above polyurethane is used.

As the oil-soluble polymer, necessary constituent materials may be used one by one, or may be used for various purposes (for example, adjustment of the glass transition temperature (Tg) of the polymer, solubility, compatibility with the dye, dispersion of the polymer, etc.). , Etc.) can be used in any ratio of two or more.

Among the oil-soluble polymers, those having the above-mentioned dissociable group are preferable, and those having at least one of a carboxyl group and a sulfonic acid group are more preferable. Those having a carboxyl group as the dissociable group are particularly preferred.

Further, after the polymerization of each of the above-mentioned polymers, an acid anhydride (for example, maleic acid or the like) acts on a reactive group such as a hydroxy group or an amino group to introduce a dissociable group by a reaction. Can also.

The content of the dissociable group is from 0.1 to
3.0 mmol / g is preferred. When the content is low, the self-emulsifying property of the polymer is low, and when the content is high, the water solubility increases, and the polymer tends to be unsuitable for dispersion.

As the dissociative group, the anionic dissociative group further includes an alkali metal (for example,
Or a salt such as an ammonium ion. Examples of the cationic group include organic acids (eg, acetic acid, propionic acid, methanesulfonic acid, etc.) and inorganic acids (eg, hydrochloric acid, sulfuric acid, etc.). , Phosphoric acid) and the like.

As the oil-soluble polymer, vinyl polymers, polyurethanes, polyesters, and the like can be used in view of imparting compatibility with the oil-soluble dye, providing excellent dispersion stability, and easy introduction of a dissociative group. And the like are particularly preferred.

Specific examples of the vinyl polymer (PA-1)
To (PA-41) are listed below. The ratios in parentheses indicate mass ratios. The present invention is not limited to these specific examples.

(PA-1) Methyl methacrylate-ethyl acrylate copolymer (50:50) (PA-2) Butyl acrylate-styrene copolymer (50:50) (PA-3) Poly n-butyl methacrylate (PA -4) polyisopropyl methacrylate (PA-5) poly (4-tert-butylphenyl acrylate (PA-6) n-butyl methacrylate-N-vinyl-
2-Pyrrolidone copolymer (90:10) (PA-7) Methyl methacrylate-vinyl chloride copolymer (70:30) (PA-8) Isobutyl methacrylate-butyl acrylate copolymer (55:45) (PA- 9) Vinyl acetate-acrylamide copolymer (8
5:15) (PA-10) n-butyl acrylate-methyl methacrylate-n-butyl methacrylate copolymer (35:
35:30) (PA-11) Ethyl methacrylate-n-butyl acrylate copolymer (70:30) (PA-12) tert-butymethacrylamide-methyl methacrylate-acrylic acid copolymer (60:30:
10) (PA-13) n-butyl acrylate-acrylic acid copolymer (80:20) (PA-14) sec-butyl acrylate-acrylic acid copolymer (85:15) (PA-15) isopropyl acrylate Acrylic acid copolymer (90:10)

(PA-16) Butyl methacrylate-2
-Hydroxyethyl methacrylate-acrylic acid copolymer (85: 5: 10) (PA-17) isobutyl methacrylate-tetrahydrofurfuryl acrylate-acrylic acid copolymer (6
0:30:10) (PA-18) n-butyl methacrylate-1H, 1
H, 2H, 2H-perfluorodecyl acrylate-acrylic acid copolymer (75: 20: 5) (PA-19) methyl methacrylate-n-butyl acrylate-acrylic acid copolymer (50: 45: 5) (PA -20) 3-methoxybutyl methacrylate-styrene-acrylic acid copolymer (35:50:15) (PA-21) ethyl acrylate-phenyl methacrylate-acrylic acid copolymer (72:25:13) (PA-22) ) Methacrylic acid ester-acrylic acid copolymer of isobutyl methacrylate-polyethylene glycol monomethyl ether (ethyleneoxy chain repeating number 23) (70:20:10) (PA-23) Ethyl methacrylate-acrylic acid copolymer (95: 5) ) (PA-24) isobutyl acrylate-methoxys Len-acrylic acid copolymer (75:15:10) (PA-25) isobutyl acrylate-N-vinylpyrrolidone-acrylic acid copolymer (60:30:10) (PA-26) 2,2,2- Tetrafluoroethyl methacrylate-methyl methacrylate-methacrylic acid copolymer (25:60:15) (PA-27) Ethyl methacrylate-2-ethoxyethyl methacrylate-methacrylic copolymer (75: 1)
5:15) (PA-28) tert-octylacrylamide-propyl methacrylate-methacrylic acid copolymer (20:
65:15) (PA-29) n-butyl methacrylate-diphenyl-2-methacryloyloxydiethylphosphonate-methacrylic acid copolymer (80: 5: 15) (PA-30) n-butyl methacrylate-phenylacrylamide-methacrylic acid Copolymer (70:15:
15)

(PA-31) n-butyl methacrylate-N-vinylpyrrolidone-methacrylic acid copolymer (7
0:15:15) (PA-32) n-butyl methacrylate-styrene sulfonic acid copolymer (90:10) (PA-33) isobutyl methacrylate-styrene sulfonic acid copolymer (90:10) (PA-34) ) N-butyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (9
0:10) (PA-35) isobutyl acrylate-n-butyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (70:20:10) (PA-36) ethyl acrylate-tert-butyl methacrylate- 2-acrylamido-2-methylpropanesulfonic acid copolymer (60:30:10) (PA-37) tert-butyl acrylate-tetrahydrofurfuryl acrylate-2-methylpropanesulfonic acid copolymer (50:40) : 10)) (PA-38) Methacrylic acid ester-2-acrylamido-2-methylpropanesulfonic acid copolymer of tert-butyl acrylate-polyethylene glycol monomethyl ether (ethyleneoxy chain repeating number 23) (60:30:10) (PA-39) Butyl acrylate-N-vinylpyrrolidone-2-acrylamido-2-methylpropanesulfonic acid copolymer (60:30:10) (PA-40) n-butylmethacrylate-2-acrylamido-2-methylpropanesulfonic acid sodium copolymer Polymer (98:12) (PA-41) n-butyl methacrylate-tert-
Butyl methacrylate-2-acrylamide-2-methylbutanesulfonic acid sodium copolymer (50: 35: 1)
5)

Specific Examples of the Condensed Polymer (PC-1)
(PC-21) is illustrated below in the form of a raw material monomer (however, PC-17 and thereafter are illustrated in the form of a polymer), but the present invention is not limited thereto.
All acidic groups in each polymer are represented in non-dissociated form.
Regarding those produced by condensation reaction of polyesters, polyamides, etc., the constituent components are all expressed as dicarboxylic acids, diols, diamines, hydroxycarboxylic acids, aminocarboxylic acids, etc., regardless of the raw materials. The ratio in parentheses means the molar percentage ratio of each component.

(PC-1) Toluene diisocyanate /
Ethylene glycol / 1,4-butanediol (50 /
(PC-2) Toluediisocyanate / hexamethylene diisocyanate / ethylene glycol / polyethylene glycol (Mw = 600) 1,4-butanediol (40/20/10/20) (PC-3) 4,4 ' -Diphenylmethane diisocyanate / hexamethylene diisocyanate / tetraethylene glycol / ethylene glycol / 2,2-bis (hydroxymethyl) propionic acid (40/10/20/2)
0/10) (PC-4) 1,5-naphthalenediisocyanate / butanediol / 4,4'-dihydroxy-diphenyl-
2,2'-propane / polypropylene glycol (Mw
= 400) / 2,2-bis (hydroxymethyl) propionic acid (50/20/5/10/15) (PC-5) isophorone diisocyanate / diethylene glycol / neopentyl glycol / 2,2-bis (hydroxymethyl) propion Acid (50/20/20
/ 10) (PC-6) diphenylmethane diisocyanate / hexamethylene diisocyanate / tetraethylene glycol / butanediol / 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid (40/10
(PC-7) terephthalic acid / isophthalic acid / cyclohexanedimethanol / 1,4-butanediol / ethylene glycol (25/25/25/15/10) (PC-
8) Terephthalic acid / isophthalic acid / 4,4'-dihydroxy-diphenyl-2,2-propane / tetraethylene glycol / ethylene glycol (30/20/20 /
15/15 /) (PC-9) Terephthalic acid / isophthalic acid / 4,4'-
Benzenedimethanol / diethylene glycol / neopentyl glycol (25/25/25/15/10) (PC-10) Terephthalic acid / isophthalic acid / 5-sulfoisophthalic acid / ethylene glycol / neopentyl glycol (24/24/2 / 25/25) (PC-11) 11-aminoundecanoic acid (100) Reaction product of (PC-12) poly (12-aminododecanoic acid) and maleic anhydride (PC-13) hexamethylenediamine / adipic acid ( (PC-14) N, N-dimethylethylenediamine / adipic acid / cyclohexanedicarboxylic acid (50/20 /
30) (PC-15) Toluene diisocyanate / 4,4'-
Diphenylmethane diisocyanate / hexamethylenediamine (30/20/50) (PC-16) hexamethylenediamine / nonamethylenediamine / urea (25/25/50)

[0145]

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The molecular weight (Mw) of the oil-soluble polymer is usually from 1,000 to 200,000,
50,000 is preferred. When the molecular weight is less than 1,000, it tends to be difficult to obtain a stable colored fine particle dispersion, and when the molecular weight exceeds 200,000, the solubility in an organic solvent becomes poor, or the viscosity of the organic solvent solution increases. Tends to be difficult to disperse.

Next, the preparation of the colored fine particle dispersion will be described. The colored fine particle dispersion can be produced by dispersing the oil-soluble dye and the oil-soluble polymer in an aqueous medium (a liquid containing at least water) in the form of colored fine particles. For example, a method in which a latex of the oil-soluble polymer is prepared in advance and the oil-soluble dye is impregnated in the latex, or a coemulsification dispersion method is used. Among these, the co-emulsification dispersion method is preferable. As the co-emulsification dispersion method, by adding water to an organic solvent containing the oil-soluble polymer and the oil-soluble dye, and, by adding the organic solvent to water, the organic solvent by A method of emulsifying and forming fine particles is more preferable.

The latex means a substance in which the oil-soluble polymer insoluble in water is dispersed as fine particles in an aqueous medium. As the dispersion state, the oil-soluble polymer is emulsified in the aqueous medium,
Any of emulsion-polymerized products, micelle-dispersed products, those in which the oil-soluble polymer has a partially hydrophilic structure in the molecule, and the molecular chains themselves are molecularly dispersed may be used.

Here, a method of preparing the polymer latex in advance and impregnating the polymer latex with the oil-soluble dye will be described. As a first example of this method, a first step of preparing a polymer latex, a second step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, and the dye solution and the polymer latex Mixing to prepare a colored fine particle dispersion. As a second example of this method, a first step of preparing a polymer latex, a dye solution in which the oil-soluble dye is dissolved in an organic solvent is prepared, and the dye solution is mixed with a liquid containing at least water. And a third step of mixing the polymer latex and the dye fine particle dispersion to prepare a colored fine particle dispersion. As a third example of this method, there is a method described in JP-A-55-139471.

Here, the emulsification dispersion method will be described. A first example of this method includes a first step of preparing a solution in which the oil-soluble dye and the oil-soluble polymer are dissolved in an organic solvent, and a solution containing the polymer and the organic solvent solution containing the dye and at least water. Mixing to prepare a colored fine particle dispersion. A second example of this method is a first step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, and a second step of preparing a polymer solution in which an oil-soluble polymer is dissolved in an organic solvent, A third step of preparing a colored fine particle dispersion by mixing the dye solution, the polymer solution, and a liquid containing at least water. A third example of this method is a first step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, and mixing the dye solution with a liquid containing at least water to prepare a dye fine particle dispersion. Dissolving an oil-soluble polymer in an organic solvent to prepare a polymer solution, mixing the polymer solution with a liquid containing at least water to prepare a polymer fine particle dispersion, and the dye fine particle dispersion the polymer A third step of preparing a colored fine particle dispersion by mixing with a fine particle dispersion. A fourth example of this method is a first step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, and mixing the dye solution and a liquid containing at least water to prepare a dye fine particle dispersion. And a second step of preparing a polymer solution in which an oil-soluble polymer is dissolved in an organic solvent, and a third step of mixing the dye fine particle dispersion and the polymer solution to prepare a colored fine particle dispersion . A fifth example of this method includes a step of directly mixing the oil-soluble dye and the oil-soluble polymer with a liquid containing at least water to prepare a colored fine particle dispersion.

The amount of the oil-soluble polymer used in the colored fine particle dispersion is preferably from 10 to 1,000 parts by mass, more preferably from 50 to 6 parts by mass, per 100 parts by mass of the oil-soluble dye.
00 parts by mass is more preferred. The amount of the polymer used is
If it is less than 10 parts by mass, fine and stable dispersion tends to be difficult, and if it exceeds 1000 parts by mass, the proportion of the oil-soluble dye in the colored fine particle dispersion is reduced, and the colored fine particle dispersion is used as an aqueous ink. When used, there is a tendency that there is no room in the formulation design.

The organic solvent used for producing the colored fine particle dispersion is not particularly limited, and can be appropriately selected based on the solubility of the oil-soluble dye or the oil-soluble polymer. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and cyclohexanone, methanol, ethanol,
-Propanol, 1-propanol, 1-butanol,
alcohol solvents such as tert-butanol; chlorine solvents such as chloroform and methylene chloride; aromatic solvents such as benzene and toluene; ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate; diethyl ether; tetrahydrofuran; And glycol-based solvents such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether. The organic solvent may be used alone or in combination of two or more, and may be a mixed solvent with water.

The use amount of the organic solvent is not particularly limited as long as the effect of the present invention is not impaired.
10 to 200 with respect to 100 parts by mass of the oil-soluble polymer.
0 mass parts is preferable and 100-1000 mass parts is more preferable. When the amount of the organic solvent used is 10 parts by mass or less, fine and stable dispersion of the colored fine particles tends to be difficult, and when the amount exceeds 2,000 parts by mass, the solvent removal for removing the organic solvent and The step of concentration becomes indispensable and complicated, and there is a tendency that there is no room in the formulation design.

When the solubility of the organic solvent in water is 10% or less, or when the vapor pressure of the organic solvent is higher than water, the organic solvent is removed from the viewpoint of the stability of the colored fine particle dispersion. Preferably. The removal of the organic solvent can be performed at 10 ° C to 100 ° C under normal pressure to reduced pressure conditions, and performed at 40 ° C to 100 ° C under normal pressure conditions or 10 ° C to 50 ° C under reduced pressure conditions.
preferable.

The colored fine particle dispersion may contain an additive appropriately selected according to the purpose. Examples of the additive include a neutralizer, a dispersant, a dispersion stabilizer, and a high-boiling organic solvent described below.

When the oil-soluble polymer has an unneutralized dissociable group, the neutralizing agent may be used to adjust the pH of the colored fine particle dispersion liquid, adjust the self-emulsifying property, impart dispersion stability, and the like. Can be used in respect. The neutralizing agent may be added at the time of taking out as a polymer before preparing the dispersion, or may be added at any step of performing the dispersion or after the completion of the dispersion. Examples of the neutralizing agent include an organic base (for example, triethanolamine, diethanolamine, N-methyldiethanolamine, dimethylethanolamine, etc.), an inorganic alkali (for an alkali metal hydroxide, For example, carbonates such as sodium hydroxide, lithium hydroxide, and potassium hydroxide include, for example, sodium carbonate, sodium hydrogen carbonate, and the like, and ammonia. For the cationic dissociable group, organic acids (for example, oxalic acid, formic acid, acetic acid, methanesulfonic acid, paratoluenesulfonic acid, etc.), inorganic acids (for example, hydrochloric acid, phosphoric acid, sulfuric acid) and the like can be mentioned. . The neutralizer has a pH of 4.5 to 10.0 from the viewpoint of improving the dispersion stability of the colored fine particle dispersion.
It is preferable to add so that the pH becomes 6.0 to 10.
More preferably, it is added so as to be 0.

The dispersant and the dispersion stabilizer may be added to any of the polymer latex, the oil-soluble polymer solution, the dye solution, a solution containing at least water, and the like. It is preferably added to the oil-soluble polymer, the dye solution, and the solution containing water in the previous step of preparing the solution. Examples of the dispersant and the dispersion stabilizer include cationic, anionic, and nonionic surfactants, and water-soluble or water-dispersible low-molecular compounds and oligomers. The addition amount of the dispersant and the dispersion stabilizer is preferably 0 to 100% by mass, and more preferably 0 to 20% by mass of the total of the oil-soluble dye and the oil-soluble polymer.
Is more preferred.

The amount of the high boiling organic solvent is preferably 1 to 1000% by mass, more preferably 10 to 400% by mass of the oil-soluble dye. The high boiling point organic solvent may be used alone or in combination of two or more.

The content of the colored fine particles in the colored fine particle dispersion is preferably from 1 to 45% by mass,
0 mass% is more preferable. The content is diluted, evaporated,
It can be adjusted appropriately by ultrafiltration or the like. The average particle size of the colored fine particles is preferably from 1 to 500 nm, more preferably from 3 to 300 nm. There are no particular restrictions on the particle size distribution, but even those with a broad particle size distribution,
It may have a monodisperse particle size distribution. The particle size and the particle size distribution can be adjusted by means such as centrifugation and filtration.

<Dye Dispersion> The dye dispersion is obtained by dispersing the oil-soluble dye dissolved in a high boiling point organic solvent in an aqueous medium. The boiling point of the high boiling organic solvent is 15
The temperature must be 0 ° C. or higher, and preferably 170 ° C. or higher. The high boiling point organic solvent has a dielectric constant of 3 to 12
, And preferably 4 to 10. The dielectric constant here indicates a relative dielectric constant at 25 ° C. in a vacuum.

The high-boiling organic solvent is not particularly limited and may be appropriately selected depending on the purpose.
Compounds described in U.S. Pat. No. 2,322,027 are exemplified, and high-boiling organic solvents such as phosphoric acid esters, fatty acid esters, phthalic acid esters, benzoic acid esters, phenols, and amides are preferable. .

As the high boiling organic solvent, the following formula [S
Compounds represented by [-1] to [S-9] are particularly preferred.

[0163]

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In the formula [S-1], R ³⁰ , R ³¹ and R ³² each independently represent an aliphatic group or an aryl group. A, b and c each independently represent 0 or 1.

In the above formula [S-2], R ³³ and R ³⁴
Each independently represents an aliphatic group or an aryl group. R ³⁵
Represents a halogen atom (F, Cl, Br, the same applies hereinafter), an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group. d represents an integer of 0 to 3. When d is plural, plural R ³⁵ may be the same or different.

In the formula [S-3], Ar represents an aryl group. e represents an integer of 1 to 6. R ³⁶ is e
And a hydrocarbon group bonded to each other by a valence hydrocarbon group or an ether bond.

In the formula [S-4], R ³⁷ represents an aliphatic group. f represents an integer of 1 to 6. R ³⁸ represents a f-valent hydrocarbon group or a hydrocarbon group bonded to each other by an ether bond.

In the formula [S-5], g is 2 to 6
Represents an integer. R ³⁹ represents a g-valent hydrocarbon group (excluding an aryl group). R ⁴⁰ represents an aliphatic group or an aryl group.

In the above formula [S-6], R ⁴¹ , R ⁴² and R ⁴³ each independently represent a hydrogen atom, an aliphatic group or an aryl group. X is, -CO- or SO ₂ - represents a.
R ⁴¹ and R ⁴² or R ⁴² and R ⁴³ may be bonded to each other to form a ring.

In the formula [S-7], R ⁴⁴ represents an aliphatic group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group or a cyano group. R ⁴⁵ represents a halogen atom, an aliphatic group, an aryl group, an alkoxy group or an aryloxy group. h represents an integer of 0 to 3. When h is plural, plural R ⁴⁵ may be the same or different.

In the above formula [S-8], R ⁴⁶ and R ⁴⁷
Each independently represents an aliphatic group or an aryl group. R ⁴⁸
Represents a halogen atom, an aliphatic group, an aryl group, an alkoxy group or an aryloxy group. i represents an integer of 0 to 4. When i is plural, plural R ⁴⁸ may be the same or different.

In the above formula [S-9], R ⁴⁹ and R ⁵⁰
Represents an aliphatic group or an aryl group. j represents 1 or 2.

In the formulas [S-1] to [S-9],
When R ^{30 to} R ³⁵ , R ³⁷ , and R ^{40 to} R ⁵⁰ are an aliphatic group or a group containing an aliphatic group, the aliphatic group may be linear, branched, or cyclic. And may contain an unsaturated bond, and may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a hydroxyl group, an acyloxy group, an epoxy group and the like.

In the formulas [S-1] to [S-9],
When R ^{30 to} R ³⁵ , R ³⁷ , and R ^{40 to} R ⁵⁰ are a cyclic aliphatic group, that is, a cycloalkyl group or a group containing a cycloalkyl group, the cycloalkyl group has 3 to 8 members. The ring may contain an unsaturated bond, and may have a substituent or a crosslinking group. Examples of the substituent include a halogen atom, an aliphatic group, a hydroxyl group, an acyl group, an aryl group, an alkoxy group, an epoxy group, and an alkyl group. Examples of the cross-linking group include a methylene group and an ethylene group. ,
And an isopropylidene group.

In the formulas [S-1] to [S-9],
When R ^{30 to} R ³⁵ , R ³⁷ , and R ^{40 to} R ⁵⁰ are an aryl group or a group containing an aryl group, the aryl group may be a halogen atom, an aliphatic group, an aryl group, an alkoxy group, an aryloxy group, an alkoxy group. It may be substituted with a substituent such as a carbonyl group.

In the formulas [S-3], [S-4] and [S-5], when R ³⁶ , R ³⁸ or R ³⁹ is a hydrocarbon group, the hydrocarbon group is It may contain a cyclic structure (for example, a benzene ring, a cyclopentane ring, or a cyclohexane ring) or an unsaturated bond, and may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an acyloxy group, an aryl group, an alkoxy group, an aryloxy group, an epoxy group, and the like.

Next, a particularly preferred high-boiling organic solvent in the present invention will be described.

In the formula [S-1], R ³⁰ , R ³¹ and R ^{32 each} represent an aliphatic group having 3 to 24 (preferably 4 to 18) carbon atoms (hereinafter abbreviated as C number). Butyl group,
2-ethylhexyl group, 3,3,5-trimethylhexyl group, n-dodecyl group, n-octadecyl group, benzyl group, oleyl group, 2-chloroethyl group, 2,3-dichloropropyl group, 2-butoxyethyl group, 2-phenoxyethyl group, cyclopentyl group, cyclohexyl group, 4-
a t-butylcyclohexyl group, a 4-methylcyclohexyl group) or an aryl group having a C number of 6 to 24 (preferably 6 to 18) (for example, phenyl, cresyl, p-nonylphenyl, xicicle, cumenyl, p-methyl); Methoxyphenyl group, p-methoxycarbonylphenyl group).
a, b and c are each independently 0 or 1, and preferably all 1.

In the above formula [S-2], R ³³ and R ³⁴
Is an aliphatic group having 4 to 24 (preferably 4 to 18) C atoms (for example, the same group as the alkyl group mentioned for R ³⁰ above)
Ethoxycarbonylmethyl group, 1,1-diethylpropyl group, 2-ethyl-1-methylhexyl group, cyclohexylmethyl group, 1-ethyl-1,5-dimethylhexyl group, 3,5,5-trimethylcyclohexyl group, 1 -Methylcyclohexyl group) or an aryl group having 6 to 24 (preferably 6 to 18) C atoms (for example, the aryl group described for R ³⁰ , 4-t-butylphenyl group, 4-t-octylphenyl group, 3,5-trimethylphenyl group, 2,4, -di-t-butylphenyl group, 2,4,-
Di-t-pentylphenyl group). R ³⁵ represents a halogen atom (preferably Cl), an alkyl group having 1 to 18 C atoms (eg, a methyl group, an isopropyl group, a t-butyl group,
-Dodecyl group), an alkoxy group having 1 to 18 carbon atoms (for example, methoxy group, n-butoxy group, n-octyloxy group,
Methoxyethoxy group, benzyloxy group), C number 6-1
8 aryloxy group (for example, phenoxy group, p-tolyloxy group, 4-methoxyphenoxy group, 4-t-butylphenoxy group) or C2-C19 alkoxycarbonyl group (for example, methoxycarbonyl group, n-butoxycarbonyl group) , 2-ethylhexyloxycarbonyl group)
Or an aryloxycarbonyl group having 6 to 25 C atoms. d is 0 or 1.

In the formula [S-3], Ar represents an aryl group having 6 to 24 (preferably 6 to 18) carbon atoms (eg, phenyl, 4-chlorophenyl, 4-methoxyphenyl, 1-naphthyl) , 4-n-butoxyphenyl group, 1,3,5-trimethylphenyl group), b is an integer of 1 to 4 (preferably 1 to 3), and R ³⁶ is e
A C 2 to C 24 (preferably 2 to 18) hydrocarbon group [e.g., the alkyl group, cycloalkyl group, aryl group,-(CH ₂ ) _2- , and the following groups described for R ³³ ,

[0181]

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Or a hydrocarbon group bonded to each other by an e-valent ether bond having 4 to 24 (preferably 4 to 18) carbon atoms [for example, -CH ₂ CH ₂ OCH ₂ CH _2- , -CH ₂
CH ₂ (OCH ₂ CH ₂ ) ₃ —, —CH ₂ CH ₂ CH ₂ OCH ₂
CH ₂ CH ₂ — and the following groups are further exemplified.

[0183]

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In the formula [S-4], R ³⁷ represents an aliphatic group having 3 to 24 (preferably 3 to 17) C atoms (for example, n
-Propyl group, 1-hydroxyethyl group, 1-ethylpentyl group, n-undecyl group, pentadecyl group, 8,9
-Epoxyheptadecyl group, cyclopropyl group, cyclohexyl group, 4-methylcyclohexyl group), and f
Is an integer of 1 to 4 (preferably 1 to 3);
³⁸ is a f-valent hydrocarbon group having 2 to 24 (preferably 2 to 18) carbon atoms or a c-valent hydrocarbon group having 4 to 24 (preferably 4 to 24 carbon atoms).
To 18) is a hydrocarbon group linked to each other by an ether bond therein (for example, the same as described as R ³⁶ group).

In the formula [S-5], g is 2 to 4
(Preferably 2 or 3) and R ³⁹Is a g-valent hydrocarbon
Element group [for example, -CH_Two-,-(CH_Two)_Two-,-(C
H_Two)_Four-,-(CH_Two)₇-, Further includes the following groups:
You.

[0186]

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R ⁴⁰ has a C number of 4 to 24 (preferably 4 to 1).
8) an aliphatic group or a C number of 6 to 24 (preferably 6 to 1);
Aryl groups of 8) (e.g., an aliphatic group as described as R ^33, an aryl group).

In the formula [S-6], R ⁴¹ represents an aliphatic group having 3 to 20 carbon atoms [eg, n-propyl, 1-ethylpentyl, n-undecyl, n-pentadecyl, 2 , 4-di-t-pentylphenoxymethyl group, 4
-T-octylphenoxymethyl group, 3- (2,4-di-t-butylphenoxy) propyl group, 1- (2,4-
A di-t-butylphenoxy) propyl group, a cyclohexyl group, 4-methylcyclohexyl) or an aryl group having a C number of 6 to 24 (preferably 6 to 18) (for example, the aryl groups mentioned above for Ar). R ⁴² and R ^{43 each} represent an aliphatic group having a C number of 3 to 24 (preferably 3 to 18) (eg, isopropyl, n-butyl, n-hexyl, 2-ethylhexyl, n-dodecyl, cyclopentyl) ,
Cyclopropyl group) or 6 to 18 carbon atoms (preferably 6 to 18 carbon atoms)
15) aryl groups (for example, phenyl group, 1-naphthyl group, p-tolyl group). R ⁴² and R ⁴³ may be bonded to each other to form a pyrrolidine ring, piperidine ring, or morpholine ring together with N, or R ⁴¹ and R ⁴² may be bonded to each other to form a pyrrolidone ring. X is -CO- or S
Represents O ₂ , preferably -CO-.

In the formula [S-7], R ⁴⁴ is an aliphatic group having 3 to 24 (preferably 3 to 18) C atoms (eg, isopropyl, t-butyl, t-pentyl, t-hexyl). Group, t-octyl group, 2-butyl group, 2-hexyl group, 2-octyl group, 2-dodecyl group, 2-hexadecyl group, t-pentadecyl group, cyclopentyl group, cyclohexyl group), C number 5 to 24 ( (Preferably 5 to 17)
(E.g., n-butoxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-
Dodecyloxycarbonyl group) an alkylsulfonyl group having 3 to 24 (preferably 3 to 18) C atoms (for example, an n-butylsulfonyl group or an n-dodecylsulfonyl group);
To 30 (preferably 6 to 24) arylsulfonyl groups (for example, p-tolylsulfonyl group, p-dodecylphenylsulfonyl group, p-hexadecyloxyphenylsulfonyl group), and a C number of 6 to 32 (preferably 6 to 24) (For example, a phenyl group and a p-tolyl group) or a cyano group.

R ⁴⁵ is a halogen atom (preferably C
l) a C number of 3 to 24 (preferably an alkyl group (e.g., alkyl groups as described as R ⁴⁴ 3 to 18)), cycloalkyl group having a C number of 5 to 17 (e.g. cyclopentyl, cyclohexyl), C Number 6 to 32 (preferably 6
To 24) aryl group (for example, phenyl group, p-tolyl group) and C1 to 24 (preferably 1 to 18) alkoxy group (for example, methoxy group, n-butoxy group, 2-ethylhexyloxy group, benzyloxy group) , N-dodecyloxy group, n-hexadecyloxy group) or C 6-32
(Preferably 6 to 24) aryloxy group (for example, phenoxy group, pt-butylphenoxy group, pt-octylphenoxy group, m-pentadecylphenoxy group,
p-dodecyloxyphenoxy group), and h is 1 to
It is an integer of 2.

In the above formula [S-8], R ⁴⁶ and R ⁴⁷
, Which are the same as R ⁴² and R ^43, R ⁴⁸ are as defined above R ^45.

In the above formula [S-9], R ⁴⁹ and R ⁵⁰
Is the same as the R ^30, R ³¹ and R ^32. j represents 1 or 2, and 1 is preferable.

The following are specific examples of the high boiling organic solvent (S-1 to S-23 as the compound represented by the above [S-1],
S-24 to S-3 as the compound represented by the above [S-2]
9. S-40 as a compound represented by the above [S-3]
To 44, S- as a compound represented by the above [S-4]
45 to 50; S-51 to S-58 as the compound represented by the above [S-5]; S-59 to 67 as the compound represented by the above [S-6]; S-68 to 75 as a compound represented by the formula, S-76 to 79 as a compound represented by the above [S-8], and S-80 to 81 as a compound represented by the above [S-9] Is shown.

[0194]

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[0195]

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[0196]

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[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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These high boiling organic solvents may be used alone or in combination of two or more.
A combination of tricresyl phosphate and dibutyl phthalate, a combination of trioctyl phosphate and di (2-ethylhexyl) sebacate, and a combination of dibutyl phthalate and poly (Nt-butylacrylamide) are exemplified.

Examples of the above-mentioned high-boiling organic solvents other than the above-mentioned compounds and / or methods for synthesizing these high-boiling organic solvents include, for example, US Pat. Nos. 2,322,027 and
No. 2,533,514, No. 2,772,163, No. 2,835,579,
No. 3,594,171, No. 3,676,137, No. 3,689,271
No. 3,700,454, No. 3,748,141, No. 3,764,
No. 336, No. 3,765,897, No. 3,912,515, No. 3,
936,303, 4,004,928, 4,080,209, 4,127,413, 4,193,802, 4,207,393
No. 4,220,711, No. 4,239,851, No. 4,278,
No. 757, No. 4,353,979, No. 4,363,873, No. 4,
430,421, 4,430,422, 4,464,464, 4,483,918, 4,540,657, 4,684,606
No. 4,728,599, No. 4,745,049, No. 4,935,
Nos. 321 and 5,013,639, EP 276,319A, 286,253A, 289,820A, 309,158A,
309,159A, 309,160A, 509,311A, 51
No. 0,576A, East German Patent No. 147,009, No. 157,147, No. 159,573, No. 225,240A, British Patent No. 2,091,124A
No., JP-A-48-47335, JP-A-50-26530, JP-A-51-25133,
No. 51-26036, No. 51-27921, No. 51-27922, No. 51-149
028, 52-46816, 53-1520, 53-1521,
53-15127, 53-146622, 54-91325, 54-1
06228, 54-118246, 55-59464, 56-64333
No. 56-81836, No. 59-204041, No. 61-84641, No.
62-118345, 62-247364, 63-167357, 63
-214744, 63-301941, 64-9452, 64-945
No. 4, No. 64-68745, JP-A No. 1-101543, No. 1-102454
No. 2-792, No. 2-4239, No. 2-43541, No. 4-2923
No. 7, No. 4-30165, No. 4-232946, No. 4-346338, etc.

In the present invention, a low-boiling organic solvent can be used in combination with the high-boiling organic solvent. The low boiling organic solvent has a boiling point of 150 ° C. or less at normal pressure (usually, about 30 ° C.).
Organic solvents such as esters (eg, ethyl acetate, butyl acetate, ethyl propionate, β-ethoxyethyl acetate, methyl cellosolve acetate), alcohols (eg, isopropyl alcohol, n-butyl alcohol, secondary butyl) Suitable examples include alcohols), ketones (eg, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone), amides (eg, dimethylformamide, N-methylpyrrolidone), and ethers (eg, tetrahydrofuran, dioxane).

[0211] The emulsification and dispersion are performed by adding
In some cases, a mixed solvent of the high-boiling organic solvent and the low-boiling organic solvent, an oil phase in which the oil-soluble dye is dissolved,
It is performed by dispersing in an aqueous phase by the aqueous medium to form minute oil droplets (the dispersed particles) of the oil phase. For the formation of the fine oil droplets (the dispersed particles) of the oil phase, a method of adding the oil phase to the aqueous phase is generally used. However, the aqueous phase is dropped into the oil phase. A so-called phase inversion emulsification method can also be preferably used.

At the time of the emulsification and dispersion, one or both of the aqueous phase and the oil phase may contain a surfactant, a wetting agent,
Additives such as dye stabilizers, emulsion stabilizers, preservatives and fungicides can be added as necessary.

Examples of the surfactant include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonic acid formalin condensates, Anionic surfactants such as oxyethylene alkyl sulfates,
Nonionics such as polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, and oxyethylene oxypropylene block copolymer Surfactants and SURFYNOLS (Ai) which are acetylene-based polyoxyethylene oxide surfactants
rProducts & Chemicals)
Amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide;
No. 157,636, pages (37) to (38), Research Disclosure No. 308119 (1989) is also preferable.

In the present invention, a water-soluble polymer can be added together with these surfactants for the purpose of stabilization immediately after emulsification. As the water-soluble polymer,
For example, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide and copolymers thereof, and natural water-soluble polymers such as polysaccharides, casein, and gelatin are preferably exemplified.

In the case of dispersing the oil-soluble dye into an aqueous ink by the emulsification dispersion, it is particularly important to control the particle size. In order to increase the color purity and density when an image is formed by an inkjet recording method, it is essential to reduce the average particle size of the dispersed particles in the dye dispersion, and the volume average particle size is preferably 100 nm or less, -50 nm is more preferable.

It was also found that the presence of coarse particles plays a very important role in printing performance. That is, it has been found that the coarse particles clog the nozzles of the head or form dirt even if they are not clogged, thereby causing non-ejection of the inkjet ink and / or skew of the ejection, which has a significant effect on printing performance. In order to prevent this, it is preferable to suppress the number of particles having a size of 5 μm or more to 10 or less and the number of particles having a size of 1 μm or more to 1000 or less in 1 μl of the ink.

As a method for removing these coarse particles, a known centrifugal separation method, microfiltration method or the like can be used. These separation means may be performed immediately after emulsification and dispersion, or may be performed immediately after filling the ink cartridge after adding various additives such as a wetting agent and a surfactant to the emulsified dispersion. As an effective means for reducing the average particle size of the dispersed particles in the dye dispersion, and eliminating coarse particles,
An emulsifying and dispersing apparatus that performs mechanical stirring can be suitably used.

As the emulsifying and dispersing apparatus, known apparatuses such as a simple stirrer, an impeller stirring method, an in-line stirring method, a mill method such as a colloid mill, and an ultrasonic method can be used. Dispersing devices are preferred, and among them, a high-pressure homogenizer is particularly preferred.

[0219] The high-pressure homogenizer is US-453.
No. 3,254, JP-A-6-47264, etc., a detailed mechanism is described, but as a commercially available device, a Gaulin homogenizer (APV GAULIN INC.),
Microfluidizer (MICROFLUIDEX
INC. ), Ultimateizer (Sugino Machine Co., Ltd.) and the like.

In recent years, US Pat.
The high-pressure homogenizer having a mechanism for atomization in an ultra-high-pressure jet stream as described in the above item is particularly effective for the emulsification and dispersion of the present invention. As an example of an emulsifying and dispersing apparatus using this ultrahigh-pressure jet stream, DeBEE2000 (BE
E INTERNATIONAL LTD. ).

The pressure for emulsifying and dispersing using the high-pressure emulsifying and dispersing apparatus is preferably 50 MPa or more (500 bar or more), and is 60 MPa or more (600 bar or more).
Is more preferable, and 180 MPa or more (1800 bar or more) is still more preferable. In the present invention, it is particularly preferable to use two or more emulsifiers in combination during the emulsification and dispersion, for example, by emulsifying with a stirring emulsifier and then passing through a high-pressure homogenizer. Further, it is also preferable that the emulsion is once emulsified and dispersed by these emulsifying apparatuses, and then an additive such as a wetting agent or a surfactant is added.

When the low-boiling organic solvent is contained in addition to the high-boiling organic solvent during the emulsification and dispersion, the low-boiling solvent is substantially removed from the viewpoint of stability and safety and health of the emulsion. Is preferred. As a method for substantially removing the low-boiling solvent, various known methods can be employed depending on the type of the low-boiling organic solvent, for example, an evaporation method, a vacuum evaporation method, an ultrafiltration method, and the like. . The step of removing the low-boiling organic solvent is preferably performed as soon as possible immediately after emulsification.

The coloring composition of the present invention can be used in various fields, and can be suitably used as an ink composition such as a water-based ink for writing, a water-based printing ink, and an ink for information recording. It can be particularly preferably used for the inkjet ink of the present invention.

(Ink for Ink Jet) The ink for ink jet of the present invention contains the coloring composition of the present invention, and may further contain other components appropriately selected as necessary. Examples of the other components include a drying inhibitor, a penetration enhancer, an ultraviolet absorber, an antioxidant, a fungicide, a pH adjuster, a surface tension adjuster, an antifoaming agent, a viscosity adjuster, a dispersant, and a dispersant. Known additives such as a stabilizer, a rust preventive, and a chelating agent are exemplified.

The above-mentioned anti-drying agent is suitably used for the purpose of preventing clogging due to drying of the ink at the ink jet opening of the nozzle used in the ink jet recording method. As the drying inhibitor, a water-soluble organic solvent having a lower vapor pressure than water is preferable. Specific examples of the drying inhibitor include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithioglycol, and 2-methyl-1,3-.
Propanediol, 1,2,3-hexanetriol,
Polyhydric alcohols represented by acetylene glycol derivatives, glycerin, trimethylolpropane, etc .; lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether; triethylene glycol monoethyl (or butyl) ether; -Heterocycles such as pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3-
Sulfur-containing compounds such as sulfolene, diacetone alcohol,
Examples thereof include polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin diethylene glycol are more preferred. These may be used alone or in combination of two or more. These anti-drying agents are preferably contained in the ink in an amount of 10 to 50 parts by mass.

Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and 1,2-hexanediol; sodium lauryl sulfate; sodium oleate; Nonionic surfactants listed as surfactants for use. These have a sufficient effect if added in an amount of 10 to 30% by mass in the inkjet ink, and are added within a range that does not cause bleeding of a print or paper-through (print-through).

The ultraviolet absorber is used for the purpose of improving the storability of an image.
Nos. 77, 61-90537 and JP-A-2-
No. 782, No. 5-1970075, No. 9-34
Benzotriazole compounds described in JP-A-557 / 057, JP-A-46-2784, JP-A-5-1944
No. 83, U.S. Pat. No. 3,214,463, benzophenone-based compounds described in JP-B-48-30492, JP-B-56-21141, and JP-A-10-881.
No. 06, etc., cinnamic acid-based compounds,
298503, 8-53427 and 8-
Nos. 339368, 10-182621, and JP-A-8-501291, and the like. 2423
Compounds described in No. 9 and compounds emitting fluorescent light by absorbing ultraviolet light represented by stilbene-based and benzoxazole-based compounds, so-called fluorescent whitening agents, and the like are also included.

The antioxidant is used for the purpose of improving the storability of an image, and examples thereof include various organic and metal complex antifading agents. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, and the like. . Examples of the metal complex-based anti-fading agent include a nickel complex, a zinc complex, and the like. No. 17643, Sections VII I through J; 15162; 18716 of 65
Page 0, left column, same No. No. 36544, page 527; Three
No. 07105, page 872; The compounds described in the patent cited in US Pat.
Preferred examples include compounds included in the general formulas and compound examples of typical compounds described on pages 127 to 137 of JP-A No. 195/1992.

Examples of the fungicide include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. Is mentioned. These are contained in the ink at 0.0
It is preferable to use 2 to 1.00% by mass.

Examples of the pH adjusting agent include hydroxides of alkali metals such as lithium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and sodium hydrogen carbonate, and the like.
Inorganic bases such as potassium acetate, sodium silicate and disodium phosphate, and organic bases such as N-methyldiethanolamine and triethanolamine are exemplified.

Examples of the surface tension modifier include nonionic, cationic and anionic surfactants. For example, the surfactant used for the above emulsification and dispersion can be used.
Those having a solubility in water at 5 ° C. of 0.5% or more are preferred.

As the dispersant and the dispersion stabilizer,
Preferable examples include the above-mentioned cations, anions, and various nonionic surfactants. Examples of the antifoaming agent include chelating agents represented by fluorine-based and silicone-based compounds and EDTA.

The pH of the inkjet ink is preferably from 6 to 10 from the viewpoint of improving storage stability.
7 to 10 are more preferred. The surface tension of the inkjet ink is preferably 20 to 60 mN / m,
25 to 45 mN / m is more preferred. The viscosity of the inkjet ink is preferably 30 mPa · s or less, more preferably 20 mPa · s or less. The inkjet ink of the present invention is suitably used in the following inkjet recording method of the present invention.

(Inkjet recording method) In the inkjet recording method of the present invention, recording is performed on an image receiving material using the inkjet ink of the present invention. In addition,
There are no particular restrictions on the ink nozzles and the like used at that time, and they can be appropriately selected according to the purpose.

-Image-Receiving Material- The image-receiving material is not particularly limited, and is a known recording material, that is, plain paper, resin-coated paper, for example, JP-A-8-1
Nos. 69172, 8-27693 and 2-2
Nos. 76670, 7-276789, 9-
323475, JP-A-62-28783, JP-A-10-153899, and 10-217
Nos. 473 and 10-235995 and 10-
JP-A-337947, JP-A-10-217597, and JP-A-10-337947, etc., include paper for exclusive use of ink jet, film, electrophotographic common paper, cloth, glass, metal, ceramics, and the like.

In the present invention, among the above-mentioned image receiving materials, a recording paper and a recording film having an image receiving layer on a support are particularly preferable.

As the support, LBKP, NBKP
Chemical pulp, GP, PGW, RMP, TMP, CT
It consists of mechanical pulp such as MP, CMP and CGP, waste paper pulp such as DIP, etc., and if necessary, mixes known additives such as pigments, binders, sizing agents, fixing agents, cationic agents, and paper strength enhancers. However, those manufactured by various apparatuses such as a fourdrinier paper machine and a round paper machine can be used, and in addition to these, synthetic paper, plastic film sheets and the like may be used. As the thickness of the support, 10 to 250
μm, and its basis weight is 10 to 250 g /
m ² is preferred.

On the support, the image receiving layer may be provided as it is, or a back coat layer may be further provided. Also, after providing a size press or an anchor coat layer with starch, polyvinyl alcohol or the like, An image receiving layer and a back coat layer may be provided. The support may be subjected to a flattening process using a calender such as a machine calender, a TG calender, and a soft calender.

Among the above-mentioned supports, paper and plastic films laminated on both sides with a polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. In the polyolefin, a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg,
It is preferable to add cobalt blue, ultramarine blue, neodymium oxide).

The image receiving layer is provided on the support,
Contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable.Examples of the white pigment include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, Preferable examples include inorganic pigments such as lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, and zinc carbonate; and organic pigments such as styrene pigment, acrylic pigment, urea resin, and melamine resin. Among these white pigments, inorganic pigments are preferable, porous inorganic pigments are more preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, any of silicic anhydride obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, but it is particularly preferable to use hydrous silicic acid.

Examples of the aqueous binder include water-soluble binders such as polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. Polymers, water-dispersible polymers such as styrene-butadiene latex, acrylic emulsions, and the like are included. These aqueous binders may be used alone or in combination of two or more. Among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are preferable in terms of adhesion to the pigment and peel resistance of the image receiving layer.

The image receiving layer may contain, in addition to the pigment and the aqueous binder, a mordant, a waterproofing agent, a lightfastness improving agent, a surfactant, and other additives.

The mordant is preferably immobilized. For this purpose, a polymer mordant is preferably used. The polymer mordant is described in
No. 28325, No. 54-74430, No. 54-124
No. 726, No. 55-22766, No. 55-14233
No. 9, No. 60-23850, No. 60-23851,
No. 60-23852, No. 60-23853, No. 60
No.-57836, No. 60-60643, No. 60-11
No. 8834, No. 60-122940, No. 60-122
No. 941, No. 60-122942, No. 60-2351
No. 34, JP-A-1-161236, U.S. Pat. Nos. 2,484,430, 2,548,564 and 31,480.
No. 61, No. 3309690, No. 4115124, No. 4124386, No. 4193800, No. 42738
No. 53, No. 4,282,305, and No. 4,450,224. An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A-1-161236 is particularly preferred. By using the polymer mordant described in the publication, an image with excellent image quality is obtained, and the light fastness of the image is improved.

The water-proofing agent is effective for making the image water-resistant, and cationic resins are particularly preferred. Examples of the cationic resin, for example, polyamide polyamine epichlorohydrin, polyethylene imine, polyamine sulfone, dimethyl diallyl ammonium chloride polymer,
Examples thereof include cationic polyacrylamide and colloidal silica, and among these, polyamide polyamine epichlorohydrin is particularly preferable. The content of these cationic resins is 1 to 15 with respect to the total solid content of the image receiving layer.
% By mass, and particularly preferably 3 to 10% by mass.

Examples of the light fastness improver include zinc sulfate, zinc oxide, hinderamine antioxidants, and benzotriazole ultraviolet absorbers such as benzophenone. Among these, zinc sulfate is particularly preferred.

The surfactant functions as a coating aid, a release improver, a slipperiness improver, or an antistatic agent. The surfactant is described in JP-A-62-1734.
Nos. 63 and 62-183457. An organic fluoro compound may be used instead of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (eg, fluorine oil), and a solid fluorine compound resin (eg, ethylene tetrafluoride resin). The above-mentioned organic fluoro compounds are described in JP-B-57-9053 (Nos. 8 to 17).
Column), JP-A-61-20994 and JP-A-62-13582.
No. 6 describes each.

Examples of the other additives include pigment dispersants, thickeners, defoamers, dyes, fluorescent brighteners, preservatives, pH adjusters, matting agents, and hardeners. .
The image receiving layer may be a single layer or two or more layers.

The thickness of the image receiving layer is 10 to 50 μm.
m is preferable and 20 to 40 μm is more preferable.

The image receiving material may be provided with a back coat layer. Examples of the components that can be added to the back coat layer include a white pigment, an aqueous binder, and other additives.

Examples of the white pigment contained in the back coat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, and the like.
Satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite,
White inorganic pigments such as aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, magnesium hydroxide, etc., organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsules, urea resin, melamine resin, etc. Is mentioned.

As the aqueous binder contained in the back coat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch,
Examples include water-soluble polymers such as cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, and polyvinylpyrrolidone, and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion.

The other components contained in the back coat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, and a waterproofing agent.

A polymer latex may be added to the constituent layers (including the back coat layer) in the image receiving material. The polymer latex is used for the purpose of improving film physical properties such as dimensional stability, curl prevention, adhesion prevention, and film crack prevention. The polymer latex is described in JP-A Nos. 62-245258 and 62-13166.
Nos. 48 and 62-11066. When a polymer latex having a low glass transition temperature (40 ° C. or less) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. When a polymer latex having a high glass transition temperature is added to the back coat layer, the back coat layer can be prevented from curling.

The ink jet recording system is not particularly limited, and is a known system, for example, a charge control system for discharging ink using electrostatic attraction, a drop-on-demand system using a vibration pressure of a piezo element (pressure pulse). method),
Acoustic ink jet method that converts electric signals into acoustic beams, irradiates the ink, and uses the radiation pressure to eject the ink,
And a thermal ink jet method in which bubbles are formed by heating the ink and the generated pressure is used. The inkjet recording method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue and different densities, and a method of colorless and transparent. A method using ink.

[0255]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “parts” and “%” represent “parts by mass” and “% by mass” unless otherwise specified.

Example 1 <Production Example 1 (Preparation of Colored Fine Particle Dispersion (B-1))> 4 parts of isopropyl alcohol, 6 parts of tert-butanol
Parts, oil-soluble polymer (PA-14 (acid content 2.07 mm
ol / g)) and 1.2 parts of an oil-soluble dye (D-4).
To 8 parts of the mixture, 2 mol / L sodium hydroxide was gradually added in such an amount that the acid of the oil-soluble polymer was neutralized.
After the temperature was increased to 30 ° C., 30 parts of water was added with stirring. This liquid was concentrated at 40 ° C. under reduced pressure to prepare a colored fine particle dispersion having a solid content of 15%. Hereinafter, this is referred to as a colored fine particle dispersion (B-1).

<Production Example 2 (Colored fine particle dispersion (B-2))
Preparation> 3 parts of ethyl acetate, 0.5 of cyclohexanone
Parts, oil-soluble polymer (PA-19 (acid content 0.69 mm)
ol / g)), and a mixed solution of 1.4 parts of the oil-soluble dye (D-4) and 0.6 part of the oil-soluble dye (D-4) was prepared. On the other hand, an amount of 2 mol / L sodium hydroxide and water 15 to neutralize the oil-soluble polymer acid is used.
Liquid mixture of 0.2 parts of sodium di (2-ethylhexyl) sulfosuccinate was prepared. The two mixed liquids were combined, mixed and emulsified with a homogenizer, and then mixed under reduced pressure.
The mixture was concentrated at 20 ° C. to prepare a colored fine particle dispersion having a solid content of 20%. Hereinafter, this is referred to as a colored fine particle dispersion (B-2).

<Production Examples 3 to 10 (Colored fine particle dispersion (B
Preparation of Colored Fine Particle Dispersions (B-3 to B-8) by Production Method 2
By a similar method to the above, a colored fine particle dispersion (B-9 to B-
10) were prepared respectively.

<Production Example 11 (Colored fine particle dispersion (B-1)
Preparation of 1))> 4 parts of isopropyl alcohol, tert
-Butanol 6 parts, oil-soluble polymer (PA-19 (acid content 0.69 mmol / g)) 1.2 parts, oil-soluble dye (D
-4) 0.5 part and exemplary high-boiling organic solvent (S-2)
To 3 parts of the mixture, 2 mol / L sodium hydroxide was gradually added in such an amount that the acid of the oil-soluble polymer was neutralized.
After the temperature was increased to 30 ° C., 30 parts of water was added with stirring. This liquid was concentrated at 40 ° C. under reduced pressure to prepare a colored fine particle dispersion having a solid content of 24%. Hereinafter, this is referred to as a colored fine particle dispersion (B-11).

<Production Example 12 (Colored fine particle dispersion (B-1)
Preparation of 2))> 4 parts of isopropyl alcohol, tert
-Butanol 6 parts, oil-soluble polymer (PC-10 (acid content 0.08 mmol / g)) 1.2 parts, oil-soluble dye (D
-4) 0.4 part and the exemplified high-boiling organic solvent (S-2)
2 mol / L in a mixture of 2 parts and 0.2 part of (S-24)
After gradually adding sodium hydroxide in an amount at which the acid of the oil-soluble polymer was neutralized, the temperature was raised to 80 ° C., and then, with stirring, 30 parts of water was added. This liquid was concentrated at 40 ° C. under reduced pressure to prepare a colored fine particle dispersion having a solid content of 30%.
Hereinafter, this is referred to as a colored fine particle dispersion (B-12).

[0261]

[Table 1]

In Table 1, "particle size (nm)"
Represents a volume average diameter (nm). (Microtrack U
PA150; value measured by Nikkiso Co., Ltd.).

<Preparation of Sample 1> In 42 parts of the colored fine particle dispersion (B-1) prepared in Production Example 1, 8 parts of diethylene glycol, 8 parts of glycerin, 5 parts of triethylene glycol monobutyl ether, 5 parts of hexaethylene glycol monosulfate, 0.5 parts of sodium dodecyl ether, di (2-
Ethylhexyl) sodium sulfosuccinate 0.5 part,
And 36 parts of ion-exchanged water were mixed and filtered through a 0.45 μm filter to prepare an aqueous inkjet ink.

<Preparation of Samples 2 to 12> In the preparation of Sample 1, except that the colored fine particle dispersion (B-1) was replaced with the colored fine particle dispersion prepared in Production Examples 2 to 12, An inkjet ink was prepared in the same manner as in Sample 1.

<Preparation of Sample 13> Oil-soluble dye (D-4)
6.28 g, sodium dioctylsulfosuccinate7.
85 g of the high-boiling point organic solvent (S-4) 7.53 g, the oil-soluble polymer (PA-19 (acid content 0.69 mmol /
g)) 18.8 g and 70 ° C. in 50 ml of ethyl acetate
And dissolved. During the dissolution, 2 mol / l sodium hydroxide was gradually added in an amount such that the acid of the oil-soluble polymer was neutralized. 500 ml of deionized water was added to this solution while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion. Next, this coarse particle dispersion was treated with a microfluidizer (MICROFLUIDEX I).
(NC) for 5 passes at a pressure of 600 bar to obtain fine particles. The resulting emulsion was desolvated with a rotary evaporator until the odor of ethyl acetate disappeared. 140 g of diethylene glycol, 50 g of glycerin, SURFYNOL 465 (AirProd) were added to the fine emulsion of the oil-soluble dye thus obtained.
octs & Chemicals) 7 g, deionized water 9
The ink was prepared by adding 00 ml.

<Preparation of Comparative Samples 1 and 2> 10 parts of diethylene glycol, 8 parts of glycerin, 10 parts of tetraethylene glycol monobutyl ether, 1 part of diethanolamine were added to 6 parts of the following comparative dye (H-1) or (H-2).
Then, 65 parts of ion-exchanged water were mixed, and the mixture was filtered through a 0.2 μm filter to prepare an inkjet ink.

<Preparation of Comparative Samples 3 to 5> Using the following oil-soluble dyes (H-3), (H-4), and (H-5), a colored fine particle dispersion ( B-13),
(B-14) and (B-15) were produced. Next, in the preparation of the sample 1, the colored fine particle dispersion (B-
An ink-jet ink was prepared in the same manner as in the preparation of Sample 1, except that 1) was replaced with (B-13), (B-14) or (B-15).

[0268]

Embedded image

<Image Recording and Evaluation> The ink jet inks obtained in each of the examples and comparative examples were evaluated as follows. The results are shown in Table 2. In Table 2, “color tone”, “paper dependence”, “water resistance”, and “light resistance” indicate that each ink-jet ink was prepared using a photo glossy paper by an ink-jet printer (manufactured by EPSON Corporation; PM-700C). (Fuji Photo Film Co., Ltd .; inkjet paper, photo grade) was evaluated after recording the image.

-Color Tone- The recorded image was observed and evaluated as A (good) and B (bad) in two steps.

-Paper Dependency-The color tone of the image formed on the photo glossy paper and the image separately formed on the plain paper for PPC are compared. When the difference between the two images is small, A (good) and The case where the difference between the images was large was evaluated as B (bad) and evaluated in two steps.

—Water Resistance— The photo glossy paper on which the image was formed was dried for 1 hour at room temperature, immersed in water for 30 seconds, allowed to dry naturally at room temperature, and observed for bleeding. A sample without bleeding was evaluated as A, a sample with slight bleeding as B, and a sample with much bleeding as C.

-Light fastness-A xenon light (850) was applied to the photo glossy paper on which the image was formed using a weather meter (Atlas CI65).
001x) for 3 days, and the image density before and after xenon irradiation was measured using a reflection densitometer (X-Rite310TR), and evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. At any concentration, the residual dye ratio of 70% or more is A; at one or two points, less than 70% is B; and at all concentrations, less than 70% is C.
Was evaluated in three steps.

[0274]

[Table 2]

As is clear from Table 2, the ink-jet ink of the present invention has a small particle size, excellent printability,
It was excellent in color development and color tone, independent of paper, and excellent in water resistance and light resistance.

Example 2 <Preparation of Sample 101> Oil-soluble dye (D-4) 6.28
g, 7.85 g of sodium dioctyl sulfosuccinate
Is 4.71 g of the exemplified high-boiling organic solvent (s-2), 7.85 g of the exemplified high-boiling organic solvent (s-11) and ethyl acetate 5
It was dissolved at 70 ° C. in 0 ml. 500 in this solution
ml of deionized water was added while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion. Next, this coarse particle dispersion is used as a microfluidizer (MICR).
5 at a pressure of 600 bar in OFLUIDEXINC)
The particles were finely divided by passing the particles twice. The solvent was removed from the resulting emulsion using a rotary evaporator until the odor of ethyl acetate disappeared. Diethylene glycol 14 was added to the fine emulsion of hydrophobic dye thus obtained.
0 g, glycerin 50 g, SURFYNOL465 (A
IrProducts & Chemicals) 7g,
900 ml of deionized water was added to prepare an ink.

<Preparation of Samples 102 to 109> Sample 101
Was prepared in the same manner as in Sample 101, except that the oil-soluble dye (D-4) was changed to the oil-soluble dye shown in Table 3.

<Preparation of Comparative Samples 110 to 112> Sample 1
01 of the compound (H-3),
Sample 10 except for changing to (H-4) and (H-5)
The same as in No. 1 was prepared.

[0279] Samples 101 to 112 thus obtained were obtained.
Was measured using Microtrac UPA (Nikkiso Co., Ltd.). The results are shown in Table 3.

Next, the ink samples 101 to 10 of the present invention were prepared.
9. Comparative Samples 110 to 112, EPSON Yellow and EPSON Light Magenta (EPSON Corporation)
Was evaluated in the same manner as in Example 1. Table 3 shows the results.

[0281]

[Table 3]

As is evident from Table 3, the ink-jet ink of the present invention was excellent in color development and color tone, small in dependence on paper, and excellent in water resistance and light resistance.

(Example 3) The same ink produced in Example 2 was used in an ink jet printer BJ-F850 (CA
Example 2) An image was printed on a photo glossy paper GP-301 of the same company using the same machine.
The same evaluation as in Example 2 was performed, and the same result as in Example 2 was obtained.

[0284]

According to the present invention, the above-mentioned conventional problems can be solved, there is no dependence on paper, excellent color development and color tone when printed on arbitrarily selected paper, handleability, odor, and safety. , Water resistance, excellent light resistance, etc., enables high recording density and high image quality, water-based ink for writing, water-based printing ink, a coloring composition suitable for information recording ink and the like, including the coloring composition, thermal It is suitable for piezoelectric, electric field or acoustic ink jet system, and when printing is performed by using a nozzle or the like, it does not cause clogging at the nozzle tip, there is no dependence on paper, and printing is arbitrarily selected on paper. It is possible to provide an ink-jet ink that is excellent in color developability and color tone, and is also excellent in water resistance and light resistance, and an ink-jet recording method capable of performing high-quality recording using the ink-jet ink.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C056 EA13 FB03 FB04 FC02 FC06 2H086 BA53 BA56 BA59 BA60 4J039 AD01 AD03 AD04 AD05 AD06 AD08 AD09 AD10 AD12 AD13 AD20 AD22 AE04 AE06 AE08 BC05 BC07 BC12 BC16 BC20 BC33 BC36 BC52 BC50 BC51 BC50 BC53 BC54 BC55 BC56 BC65 BC74 BC76 BE07 CA06 DA02 EA35 EA38 EA41 EA42 EA44 GA24

Claims (9)

[Claims] 1. A coloring composition comprising an oil-soluble dye represented by the following formula (I). Formula (I) In the formula (I), Q represents an atomic group necessary for the compound represented by the formula (I) to have absorption in a visible region and / or a near infrared region. R ₁ represents an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, a sulfamoyl group, or a phosphinyl group. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R ₂ and R ₃ may combine with each other to form a ring structure. 2. The coloring composition according to claim 1, wherein the oil-soluble dye is dispersed in an aqueous medium. 3. A boiling point of 150 ° C. or higher and 25 ° C.
The colored composition according to claim 2, comprising a dye dispersion obtained by dispersing an oil-soluble dye dissolved in a high boiling point organic solvent having a relative dielectric constant of 3 to 12 in an aqueous medium. 4. The colored composition according to claim 2, comprising a colored fine particle dispersion in which colored fine particles containing an oil-soluble dye and an oil-soluble polymer are dispersed in an aqueous medium. 5. The colored composition according to claim 4, wherein the colored fine particle dispersion contains a high-boiling organic solvent. 6. The colored composition according to claim 4, wherein the colored fine particles comprise an oil-soluble dye dispersed in an oil-soluble polymer. 7. The coloring composition according to claim 1, which is used for an ink composition. 8. An ink-jet ink comprising the coloring composition according to claim 1. Description: 9. An ink jet recording method, wherein recording is performed using the ink for ink jet according to claim 8.