JP2001262039A - Colored fine particle dispersion, ink-jet recording ink using the same and ink-jet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored fine particle dispersion which has a small particle diameter of colored fine particles and, simultaneously, excels in dispersion stability, has small paper dependence and excels in color developability/tone in printing on any selected paper and, at the same time, water resistance and light-resistance. SOLUTION: The colored fine particle dispersion comprises colored fine particles containing an oil-soluble dye which is preferably represented by formula (I) [wherein Q is an atom group necessary for the compound represented by formula (I) to have an absorption in the visible region and/or the near infrared region; A is -NR4R5 or a hydroxy group; R4 and R5 are each independently a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; B1 is =C(R6)- or =N-; B2 is -C(R7)= or =N-; and R2, R3, R6, and R7 are each independently a hydrogen atom or a substituent] and a terminal-dissociative vinyl polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous colored fine particle dispersion containing an oil-soluble dye, an ink jet recording ink containing the colored fine particle dispersion, and ink jet recording using the ink jet recording ink. About the method.

[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 inks for inkjet recording, oil-based inks, aqueous inks, and solid inks are known.Among these, aqueous inks are advantageous in terms of ease of production, handleability, odor, safety, and the like. Water-based inks have become mainstream.

However, most of the aqueous inks use water-soluble dyes that dissolve in a molecular state, and thus have the advantage of high transparency and color density. However, since the dyes are water-soluble, they have poor water resistance. When printing on so-called plain paper, there is a problem that bleeding occurs and the printing quality is remarkably deteriorated and 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, although the water resistance is improved to some extent, it is not sufficient, and the storage stability of the dispersion of the pigment or disperse dye in the water-based ink is lacking, and clogging at the ink ejection port occurs. There is a problem that it is easy. In addition, these water-based 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. Also, JP-A-11-140362
In Japanese Patent Application Laid-Open Publication No. H11-146, a method is proposed in which a latex polymerized in the presence of a carboxylic acid and a chain transfer agent is aggregated with a colorant. However, in the case of the inkjet ink obtained by the above method, the color tone is insufficient, the color reproducibility 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. There is a problem that the nature is not always enough.

[0006] Japanese Patent Application Laid-Open Nos. 9-59552 and 9-1
No. 11163, No. 9-255887, No. 10-367
JP-A Nos. 28 and 11-286637 disclose that the above color tone can be improved by using a dye obtained by coupling an aromatic diamine to a color photographic coupler. However, in these, the particle size or particle size distribution of the dispersion tends to be large, and the dispersion stability and printability are not sufficient, and there is a problem that the color tone changes depending on the type of image receiving paper.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention has a small particle diameter of the colored fine particles, and is excellent in dispersion stability, less dependent on paper, and excellent in color developability and color tone when printed on arbitrarily selected paper, and water resistance. It is an object of the present invention to provide a colored fine particle dispersion which is excellent in light fastness and is suitable for an aqueous ink for writing, an aqueous printing ink, an ink for information recording and the like. Further, the present invention is suitable for thermal, piezoelectric, electric field or acoustic ink jet systems, and when performing printing or the like using a nozzle or the like, the occurrence of clogging at the nozzle tip is small, the paper dependence is small, and any It is an object of the present invention to provide an ink jet recording ink and an ink jet recording method which are excellent in color developability and color tone when printing on paper selected as described above, and are also excellent in water resistance and light resistance.

[0008]

Means for solving the above problems are as follows. That is, <1> a colored fine particle dispersion containing colored fine particles containing an oil-soluble dye and a terminal dissociable vinyl polymer. <2> The colored fine particle dispersion according to <1>, wherein the terminal dissociable vinyl polymer has a dissociable group content of 0.1 to 2.0 mmol / g. <3> The above <1>, wherein the dissociable group of the terminal dissociable vinyl polymer is carboxylic acid or sulfonic acid.
> Or <2>. <4> The colored fine particle dispersion according to any one of <1> to <3>, wherein the oil-soluble dye is represented by the following general formula (I).

Formula (I)

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In the formula, Q represents an atomic group necessary for the compound represented by the general formula (I) to have absorption in a visible region and / or a near infrared region, and A represents —NR ⁴ R ⁵ or a hydroxy group. Wherein R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;
B ¹ represents = C (R ⁶ )-or = N-, and B ² represents -C
(R ⁷⁾ = or represents -N =, represent R ^2, R ^3, R ⁶ and R ⁷ each independently represent a hydrogen atom or a substituent.
R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ^6, and R ⁶ and R ⁷ may combine with each other to form a ring.

<5> Dispersed particles are produced by adding water to an organic solvent phase containing a terminally dissociable vinyl polymer and an oil-soluble dye or emulsifying the same by adding the organic solvent phase to water. <1.
> The colored fine particle dispersion according to <4>. <6> An ink jet recording ink comprising the colored fine particle dispersion according to any one of <1> to <5>. <7> An ink jet recording method, wherein recording is performed using the ink for ink jet recording according to <6>.

In the present invention, the following means are preferably included. <8> The above-mentioned, wherein the terminal dissociable vinyl polymer is produced by chain transfer polymerization in the presence of at least one selected from carboxylic acids having a mercapto group, sulfonic acids having a mercapto group, and salts thereof. <
2>. <9> The terminal-dissociable vinyl polymer produced by chain transfer polymerization in the presence of at least one selected from mercaptoacetic acid, 2-mercaptoethanesulfonic acid, mercaptosuccinic acid and salts thereof. The colored fine particle dispersion according to <2>. <10> An ink jet recording ink comprising the colored fine particle dispersion according to any one of <8> to <9>.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The colored fine particle dispersion, the ink for ink jet recording and the ink jet recording method of the present invention will be described below. (Colored Fine Particle Dispersion) The colored fine particle dispersion of the present invention is obtained by dispersing colored fine particles containing an oil-soluble dye and a terminal-dissociable vinyl polymer in an aqueous medium.

-Oil-Soluble Dye- Among the oil-soluble dyes usable in the present invention, any yellow dye can be used. For example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or hetenylazo dyes having open-chain active methylene compounds as coupling components; azomethine dyes having open-chain active methylene compounds as coupling components; Methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes, anthraquinone dyes and the like; other dyes include quinophthalone dyes, nitro-nitroso dyes, acridine dyes Acridinone dyes and the like can be mentioned.

Among the oil-soluble dyes usable in the present invention, any magenta dye can be used. For example, aryl or hetarylazo dyes having phenols, naphthols and anilines as coupling components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupling components;
For example, arylidene dyes, styryl dyes, merocyanine dyes, methine dyes such as oxonol dyes; diphenylmethane dyes, triphenylmethane dyes, carbonium dyes such as xanthene dyes, such as quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, Examples include condensed polycyclic dyes such as dioxazine dyes.

As the cyan dye among the oil-soluble dyes that can be used in the present invention, any dye can be used.
For example, an indaniline dye, an indophenol dye or an azomethine dye having a pyrrolotriazole as a coupling component; a polymethine dye such as a cyanine dye, an oxonol dye, or a merocyanine dye; a carbonium dye such as a diphenylmethane dye, a triphenylmethane dye, or a xanthene dye A phthalocyanine dye;
Anthraquinone dyes; examples of the coupling component include aryl or hetenylazo dyes having phenols, naphthols, and anilines, and indigo / thioindigo dyes.

Each of the above-mentioned dyes may exhibit each color of yellow, magenta and cyan only after a part of the chromophore dissociates, and in this case, the counter cation is an inorganic metal such as an alkali metal or ammonium. It may be a cation, an organic cation such as a pyridinium or quaternary ammonium salt, or a polymer cation having such a partial structure.

Among them, a dye formed from a coupler and a developing agent in a photographic material is effective. As such a dye, a dye represented by the following formula (I) is preferable.

Formula (I)

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In the general formula (I), A represents —NR ⁴ R ⁵ or a hydroxy group, and R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Specifically, R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl,
n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl group (preferably substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms) For example, cyclohexyl, cyclopentyl,
4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms) For example, bicyclo [1,2,2] heptane-
2-yl, bicyclo [2,2,2] octan-3-yl), and a tricyclo structure having many ring structures. An alkyl group (for example, an alkyl group of an alkylthio group) among the substituents described below also represents an alkyl group having such a concept. An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-
Hexadecanoylaminophenyl) or a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound obtained by removing one hydrogen atom from a monovalent group; Preferably, it has 3 carbon atoms.
To 30 5- or 6-membered aromatic heterocyclic group.
For example, it represents 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl).

When R ⁴ and R ⁵ are an alkyl group, an aryl group or a heterocyclic group, the groups represented by R ⁴ and R ⁵ may further have a substituent. Preferred substituents include 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, a cyano group, Hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocycle O group, sulfamoyl group, sulfo group, alkyl and aryl sulfinyl group, alkyl and aryl sulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl Groups, phosphinyloxy groups, phosphinylamino groups and silyl groups.

More specifically, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [linear,
Represents a branched or cyclic substituted or unsubstituted alkyl group.
Alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl),
A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably substituted with 5 to 30 carbon atoms) Alternatively, it is an unsubstituted bicycloalkyl group, 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] heptan-2-yl, bicyclo [ 2,
2,2] octan-3-yl), and a tricyclo structure having more ring structures. An alkyl group (for example, an alkyl group of an alkylthio group) among the substituents described below also represents an alkyl group having such a concept. ],

Alkenyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably substituted or unsubstituted having 3 to 30 carbon atoms); A cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms, for example, 2-
Cyclopenten-1-yl, 2-cyclohexen-1-
Yl), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably having 5 to 30 carbon atoms)
Is a substituted or unsubstituted bicycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkene having one double bond. For example, bicyclo [2,
2,1] hept-2-en-1-yl, bicyclo [2,
2,2] oct-2-en-4-yl)], alkynyl group (preferably substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group,

An aryl group (preferably having 6 to 30 carbon atoms)
A substituted or unsubstituted aryl group such as phenyl,
p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and one hydrogen atom It is a monovalent group from which atoms have been removed, and more preferably has 3 to 30 carbon atoms.
Is a 5- or 6-membered aromatic heterocyclic group. For example,
2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, , Methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy),
Aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy ), A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms). Ring oxy group, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy),

Acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyl Oxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having 2 carbon atoms) 0 substituted or unsubstituted alkoxycarbonyloxy group, for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably having 7 to 30 carbon atoms, An unsubstituted aryloxycarbonyloxy group, for example, phenoxycarbonyloxy, p-
Methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms;
A substituted or unsubstituted anilino group having 6 to 30 carbon atoms,
For example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, carbon number 1)
To 30 substituted or unsubstituted alkylcarbonylamino groups, substituted or unsubstituted arylcarbonylamino groups having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino,
Benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino, N, N-dimethylaminocarbonylamino,
N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino , N-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p -Chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino),

Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octyl Aminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methylsulfonylamino, Butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, If example methylthio, ethylthio, n
-Hexadecylthio), an arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms,
For example, phenylthio, p-chlorophenylthio, m-
Methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group ( Preferably, a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3
-Dodecyloxypropyl) sulfamoyl, N, N-
Dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), a sulfo group,

Alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl) , P
-Methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably 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, ethylsulfonyl Phenylsulfonyl, p-methylphenylsulfonyl), an acyl group (preferably 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, For example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p-n-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably,
A substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-
Chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably having 2 to 30 carbon atoms)
Substituted or unsubstituted alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl),

Carbamoyl group (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example,
Carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably having 6 to 30 carbon atoms)
Or a substituted or unsubstituted arylazo group having 3 to 30 carbon atoms, for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo) Imide group (preferably N-succinimide, N-phthalimido), phosphino group (preferably having 2 to 30 carbon atoms).
Or a substituted or unsubstituted phosphino group, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl, dioctyl) Oxyphosphinyl,
Diethoxyphosphinyl), a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), A phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example,
Dimethoxyphosphinylamino, dimethylaminophosphinylamino) and a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl). Can be

A is preferably -NR ⁴ R ⁵ . R
⁴ and R ⁵ are each independently preferably a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, more preferably a hydrogen atom, an alkyl group or a substituted alkyl group, and the number of carbon atoms is 1 to
Most preferably, it is an alkyl group of 18 or a substituted alkyl group having 1 to 18 carbon atoms.

In the general formula (I), B ¹ is ＝ C (R ⁶ )-
Or = N- to represent, B ² is -C (R ⁷⁾ = or -N
= Represents Preferably if B ¹ and B ² will not become -N = simultaneously, B ¹ is ^{= C (R 6) -,} B 2 is -C
It is more preferable that (R ⁷ ) =.

In the general formula (I), R ² , R ³ , R
⁶ and R ⁷ each independently represent a hydrogen atom or a substituent. The substituent is preferably a substituent having 1 to 30 carbon atoms, and specific examples are the same as the substituents of the groups represented by R ⁴ and R ⁵ .

R ² is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an acylamino group, or a ureido group, more preferably a hydrogen atom and 1 to 3 carbon atoms.
Is an alkyl group.

R ³ , R ⁶ and R ^{7 each} represent a hydrogen atom,
To 20 alkyl groups, alkoxy groups, acylamino groups,
A ureido group is preferable, more preferably a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom.

Note that R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵
And R ⁶ and R ⁶ and R ⁷ may combine with each other to form a ring.

In the general formula (I), Q represents an atomic group necessary for the compound represented by the general formula (I) to have absorption in a visible region and / or a near infrared region. )
The group represented by-(Cp-28) is preferable as the group represented by Q. The groups represented by (Cp-1) to (Cp-28) bind to a part other than Q in the general formula (I) at the position of *.

[0037]

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[0038]

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[0039]

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Hereinafter, (Cp-1) to (Cp-28) will be described in detail. In formula (Cp-1), R ₅₁ represents an alkyl group, an aryl group, a heterocyclic group, or an alkoxy group, and R ₅₂ represents a carbamoyl group or a cyano group. Preferably, R ₅₁ is a t-butyl group, a 1-ethylcyclopropyl group, a 1-methylcyclopropyl group, a 1-benzylcyclopropyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted indolinin-1-yl. Group,
And a substituted or unsubstituted indol-3-yl group, and R ₅₂ represents an N-arylcarbamoyl group or a cyano group.

In the formula (Cp-2), R ₅₃ represents an aryl group or a heterocyclic group, and R ₅₂ represents a group having the same meaning as R ₅₂ in (Cp-1). Preferably, R ₅₃ is a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group (particularly preferably, thiazol-2-yl, benzothiazol-2-yl, oxazol-2-yl, benzoxazol-2). -Yl, 1,2,4-oxadiazol-3 (or 5) -yl, 1,3,4-oxadiazol-2 (or 5) -yl, 1,2,4-thiadiazole-3 (or 5) -yl, 1,3,4-thiadiazol-2 (or 5) -yl, pyrazol-3-yl, indazol-3-yl, 1,2,4-triazol-3-yl, 2-pyridyl, -Pyrimidinyl, 2-
Pyrazinyl, quinazolin-2-yl or quinazolin-4-yl), and R ₅₂ represents a cyano group.

In the formula (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 alkoxycarbonyl group. Represents an amino group. R ₆₂ represents an alkyl group, an aryl group or a heterocyclic group. Preferably, R
₆₁ represents an alkyl group, an acylamino group, an amino group, an amino carbonyl amino group or an alkoxycarbonylamino group,, R ₆₂ represents an aryl group or a heterocyclic group, more preferably, R ₆₁ is an acylamino group or an N- arylamino R ₆₂ represents an aryl group.

In the formulas (Cp-4) and (Cp-5), R ₆₃ and R ₆₄ are each 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, an alkoxy group, an aryloxy group, an aminocarbonylamino group or an alkoxycarbonylamino group. Preferably, R ₆₃ is an alkyl group,
Represents an aryl group, an alkoxy group or an aryloxy group, R ₆₄ represents an alkyl group or an aryl group, particularly preferably, R ₆₃ represents a methyl group, a t-butyl group or a substituted or unsubstituted phenyl group.

In the formulas (Cp-6) and (Cp-7), R ₆₃ represents a group having the same meaning as described above, and R ₆₅ , R ₆₆ and R ₆₇ each represent a hydrogen atom, an alkyl group, an aryl group, Represents a ring group, acylamino group, alkyl or arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxy group, aryloxy group, aminocarbonylamino group, alkoxycarbonylamino group, acyl group, alkoxycarbonyl group or carbamoyl group . Preferably, R ₆₃ is an alkyl group, an aryl group,
An alkoxy group or an aryloxy group, R _65, R
₆₆ and R ₆₇ each represent a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group or a carbamoyl group.

In the formula (Cp-8), R ₆₈ and R ₆₉
Are hydrogen, alkyl, aryl, heterocyclic, acylamino, alkyl or arylsulfonylamino, amino, alkylthio, arylthio, alkoxy, aryloxy, aminocarbonylamino, alkoxycarbonylamino, respectively. Represents a group, an acyl group, an alkoxycarbonyl group or a carbamoyl group. Preferably, R ₆₈ and R ₆₉ each represent a hydrogen atom, an alkyl group or an aryl group.

The formulas (Cp-9), (Cp-10) and (Cp
-11) and (Cp-12), R ₇₀ represents an alkyl group, an aryl group or a heterocyclic group, and R ₇₁ represents a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, an acylamino group, an alkyl group, Arylsulfonylamino group, amino group, aminocarbonylamino group,
An alkylthio group, an arylthio group, an alkoxy group or an alkoxycarbonyl amino group, R ₇₂ and R ₇₃
Represents a hydrogen atom or an alkyl group, 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. When a, b, or c is plural, plural R ₇₁ may be the same or different. Preferably, R ₇₀ represents an alkyl group or an aryl group, R ₇₁ represents a halogen atom, an alkyl group or an acylamino group, R ₇₂ and R ₇₃ each represent a hydrogen atom, a methyl group or an ethyl group; Or 2; b represents 1 or 2; c
Represents an integer of 0 to 2.

In the formula (Cp-13), 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 or arylsulfonylamino group; ₇₅ is a halogen 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, an alkoxy group, an aryloxy group, an aminocarbonylamino group or an alkoxycarbonylamino group And d is 0
Represents an integer of any of 1 to 4. When d is plural, plural R ₇₅ may be the same or different. Preferably, R ₇₄ represents a carbamoyl group, a sulfamoyl group or an acylamino group, R ₇₅ represents an acylamino group, an alkyl or arylsulfonylamino group, an aminocarbonylamino group or an alkoxycarbonylamino group, and d represents 0 or 1.

In the formula (Cp-14), R ₇₅ and d
Represents the same meaning as described above, R ₇₈ and R ₇₉ represent groups having the same meaning as R _75, and R ₇₆ and R ₇₇ represent a cyano group, a sulfamoyl group, an alkyl or aryl sulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. Represents a group. Preferably, R ₇₅ represents a halogen atom, an alkyl group or an aryl group, d represents an integer from 0 to 2, R ₇₈ and R ₇₉ represent a halogen atom, an alkyl group or an aryl group, R ₇₆ and R ₇₇ represents a cyano group.

In the formula (Cp-15), R ₇₅ and d
Represents the same meaning as described above, and R ₈₀ and R ₈₁ represent a cyano group,
Represents a sulfamoyl group, an alkyl or arylsulfonyl group, an acyl group, an alkoxycarbonyl group or a carbamoyl group. Preferably, R ₇₅ represents a halogen atom, an alkyl group or an aryl group, d represents an integer from 0 to 2, and R ₈₀ and R ₈₁ represent a cyano group.

In the formula (Cp-16), R ₈₂ , R ₈₃ and R ₈₄ each represent a hydrogen atom, an alkyl group, an aryl group,
Heterocyclic group, acylamino group, alkyl or arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxy group, aryloxy group, aminocarbonylamino group, alkoxycarbonylamino group,
Represents an acyl group, an alkoxycarbonyl group or a carbamoyl group.

In the formula (Cp-17), R ₈₅ and R
₈₆ is 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, an alkoxy group, an aryloxy group, an aminocarbonylamino group, an alkoxycarbonyl group, respectively. Represents an amino group, an acyl group, an alkoxycarbonyl group or a carbamoyl group. Preferably, R ₈₅ and R ₈₆ each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, or an alkyl or arylsulfonylamino group.

In the formulas (Cp-18) to (Cp-20), R ₈₇ and R ₈₈ represent a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a sulfamoyl group, an alkane sulfonyl group, an arenesulfonyl group or a nitro group. R ₈₉ and R ₉₀ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Preferably, R ₈₇ represents a carbamoyl group, an alkoxycarbonyl group or a cyano group, R ₈₈ represents a carbamoyl group, an alkoxycarbonyl group, a cyano group or an alkyl and arylsulfonyl group, and R ₈₉ and R ₉₀ each represent an alkyl group or Represents an aryl group. More preferably, R ₈₇ represents a cyano group, R ₈₈ represents an alkoxycarbonyl group, and R ₈₉ and R ₉₀ represent an aryl group.

In the formulas (Cp-21) to (Cp-26), R ₉₁ and R ₉₂ are an alkyl group, an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a sulfamoyl group. ,
Represents an alkanesulfonyl group, an arenesulfonyl group or a nitro group, and R ₉₃ , R ₉₄ and R ₉₅ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkyl or Represents an arylsulfonylamino group, a halogen atom, an amino group, an alkylthio group, an arylthio group, an alkoxy group or an aryloxy group. Preferably, R ₉₁ represents an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group or a cyano group;
₉₂ represents a carbamoyl group, an alkoxycarbonyl group, a cyano group, a sulfamoyl group or an alkyl or arylsulfonyl group, and R ₉₃ , R ₉₄ and R ₉₅ each represent a hydrogen atom, an alkyl group, an acylamino group, a halogen atom,
Represents an amino group, an alkylthio group or an arylthio group.

In the formula (Cp-27), R ₉₇ , R ₉₈ and R ₉₉ each represent a hydrogen atom, a cyano group, a sulfamoyl group, an alkyl or arylsulfonyl group, an acyl group, an alkoxycarbonyl group or a carbamoyl group; ₉₆ represents an amino group, an alkylthio group, an arylthio group, an alkoxy group or an aryloxy group. Preferably, R ₉₇ , R ₉₈ and R ₉₉ each represent a hydrogen atom or a cyano group, and R ₉₆ represents an N-arylamino group.

In the formula (Cp-28), R ₁₀₀ and R ₁₀₁ each represent a hydrogen atom, a perfluoroalkyl group, a cyano group, a nitro group, a sulfamoyl group, an alkyl or arylsulfonyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group. And R ₁₀₂ represents an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, an alkyl or aryl sulfonyl group, an acyl group, an alkoxycarbonyl group or a carbamoyl group. Preferably, R ₁₀₀ and R
₁₀₁ represents a hydrogen atom, a perfluoroalkyl group, a cyano group, a nitro group, an alkyl and arylsulfonyl group, an alkylthio group or an arylthio group;
₁₀₂ represents an aryl group or a heterocyclic group.

R _{51 to} R ₅₃ , R _{61 to} R ₆₉ , and R _{70 to} R
Specific examples of preferred groups exemplified in the description of ₁₀₂ are the same as those exemplified as the substituents of the groups represented by R ⁴ and R ⁵ . The groups represented by R _{51 to} R ₅₃ , R _{61 to} R ₆₉ , and R _{70 to} R ₁₀₂ may further have a substituent, and preferred substituents are those represented by R ⁴ and R ^5. The same as the substituents described above.

Of the groups represented by the formulas (Cp-1) to (Cp-28), (Cp-1), (Cp-2) and (Cp-
4), (Cp-5), (Cp-11), (Cp-1)
2), (Cp-18), (Cp-21) and (Cp-
22) are preferred, and particularly, the magenta dye is a pyrazolotriazole azomethine compound represented by the general formula (I) or (Cp-4), and the cyan dye is a general formula (I) or (Cp-18). Most preferred are pyrrolotriazole azomethine compounds.

Further, the compounds represented by the general formulas (I) and (Cp-18)
R of the pyrrolotriazoleazomethine compound represented by
^{When 87} is an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.30 or more, the absorption is sharp, and it is more preferable. And, R of the pyrrolotriazole azomethine compound
The sum of Hammett's substituent constant σ _p values of ⁸⁷ and R ⁸⁸ is 0.7
Those having 0 or more exhibit an excellent hue as a cyan color, and are more preferable.

For further details on hue, refer to Japanese Patent Application No.
-365188 as described in the specification.

The oil-soluble azomethine dye represented by the general formula (I) has a total number of carbon atoms of 8 to 4 as a substituent.
It is preferred to have at least one, preferably 10 to 30, diffusion resistant groups. The oil-soluble azomethine dye represented by the general 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 out of the range.

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

Specific examples of the oil-soluble azomethine dyes represented by the formula (I) (Exemplary compounds D-1 to D-3)
4, exemplified compounds M-1 to 16 and exemplified compounds C-1
Although 9) is shown, the oil-soluble dye used in the present invention is not limited to these.

[0063]

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[0066]

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[0068]

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[0069]

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[0070]

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[0071]

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[0073]

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[0074]

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[0075]

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[0076]

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[0079]

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Specific examples of the dye represented by formula (I) are further described in JP-A-11-365187 and JP-A-11-365187.
-365188, but is not limited thereto.

The dyes represented by formula (I) are described in JP-A-4-126772, JP-A-5-177959, and JP-A-9-2.
No. 92679, No. 10-62926, No. 11-158
No. 047, Japanese Patent Publication No. Hei 7-94180, and Japanese Patent Application Nos. 11-365187 and 11-365188.

-Terminal dissociable vinyl polymer- In the present invention, the term "terminal dissociable vinyl polymer" means a polymer having an anionic dissociable group at one end of a vinyl polymer chain or one of two vinyl polymer chains. And a polymer having an anionic dissociative group at one end of the vinyl polymer chain from the viewpoint of stabilizing the dispersion.

The dissociable group of the terminal dissociable vinyl polymer is not particularly limited, and the vinyl polymers having various anionic dissociable groups can be used. For example, a carboxylic acid group, a thiocarboxylic acid group, a carbodithioic acid group, a sulfonic acid group, a sulfinic acid group, a sulfuric acid monoester group, a phosphoric acid group, and the like, and a carboxylic acid group, a sulfonic acid group, and a sulfuric acid monoester group are preferable. Carboxylic acid groups and sulfonic acid groups are more preferred.

The terminal dissociable vinyl polymer can be synthesized by a conventionally known method. For example, it can be synthesized by a method of introducing a dissociable group at the time of polymerization, a method of introducing a functional group that is not a dissociable group at the time of polymerization, and converting the functional group to a dissociable group by a chemical reaction. As a method for introducing a dissociable group during polymerization, a method for radically polymerizing a vinyl monomer using a chain transfer agent having a dissociable group, a polymerization initiator or an iniferter, and a method for dissociating a dissociable group into an initiator and / or a terminator are used. And a method of ionic polymerization using a compound having the same. As a method of introducing a functional group which is not a dissociable group and converting it into a dissociable group by a chemical reaction, a vinyl monomer is radically polymerized or initiated using a chain transfer agent having a functional group, a polymerization initiator or an iniferter. Using a compound having a functional group as either an agent and / or a terminator, a prepolymer is synthesized by ionic polymerization and deprotected (for example,
A method of reacting the prepolymer with a compound having a dissociating group (for example, a reactive group such as a hydroxyl group or an amino group remaining at the terminal)
A method of reacting a compound having an acid anhydride (for example, maleic anhydride) or the like;

The synthesis of the terminal dissociable vinyl polymer usable in the present invention is described in “Synthesis and Reaction of Polymer (1)” (edited by The Society of Polymer Science, published by Kyoritsu Shuppan Co., Ltd. (199)
2))), "Precision Polymerization (edited by The Chemical Society of Japan, published by The Society for the Promotion of Science (1993))", "Synthesis and Reaction of Polymers (1)
(Edited by the Society of Polymer Science, published by Kyoritsu Shuppan Co., Ltd. (1995)) "
A known method described in, for example, can be used.

Examples of the chain transfer agent include those having a dissociable group, such as mercaptoacetic acid, 2-mercaptopropionic acid, 2-mercaptosuccinic acid, 4 (2-mercaptoethyloxy) benzoic acid, and 2-mercaptoethane. Sulfonic acid, 2-mercaptopropanesulfonic acid, 2,3
-Dimercapto-1-propanesulfonic acid, and salts thereof. On the other hand, as chain transfer agents having a functional group other than the dissociative group, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 2,2
Examples include 3-dimercapto-1-propanol, 2-aminoethanethiol, and mercaptoacetic ester. Among the chain transfer agents, mercaptoacetic acid, 2-mercaptopropionic acid, 2-mercaptosuccinic acid, 2-mercaptosuccinic acid,
Mercaptoethanesulfonic acid and salts thereof are preferred, and mercaptoacetic acid, 2-mercaptosuccinic acid,
Mercaptoethanesulfonic acid and salts thereof are more preferred.

Examples of the polymerization initiator include those having a dissociative group, such as 2,2'-azobis (2-methylpropanoic acid), 4,4'-azobis (4-cyanopentanoic acid), and persulfate. Potassium and the like. As those having a functional group other than the dissociable group, 2,2′-azobis [2
-(Hydroxymethyl) propionitrile], 2,2 '
-Azobis [2-methyl-N- (2-hydroxyethyl) -propanoic acid amide] and the like.

Examples of the vinyl monomer include the following. Acrylic esters and methacrylic esters (ester groups are aliphatic groups and aromatic groups, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-
Butyl, tert-butyl, amyl, hexyl, 2-ethylhexyl, tert-octyl, 2
-Chloroethyl group, 4-bromobutyl group, cyanoethyl group, 2-acetoxyethyl group, furfuryl group, tetrahydrofurfuryl group, 5-hydroxypentyl group, cyclohexyl group, benzyl group, hydroxymethyl group, butoxymethyl group, 3-methoxybutyl Group, 2- (2-methoxyethoxy) ethyl group, 2- (2-butoxyethoxy)
Ethyl group, 2,2,2-tetrafluoroethyl group, 1
H, 1H, 2H, 2H-perfluorodecyl group, phenyl group, 2,4,5-tetramethylphenyl group, 4-chlorophenyl group, etc.);

Vinyl esters, specifically, an aliphatic carboxylic acid vinyl ester which may have a substituent (for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate) , Vinyl chloroacetate, etc.), and optionally substituted aromatic carboxylic acid vinyl esters (eg, vinyl benzoate, vinyl 4-methylbenzoate, vinyl salicylate, etc.);

Acrylamides, specifically, acrylamide, N-monosubstituted acrylamide, N-disubstituted acrylamide (substituents are aliphatic groups, aromatic groups, and silyl groups, for example, methyl group, ethyl group, n-group A propyl group,
Isopropyl group, n-butyl group, tert-butyl group,
tert-octyl group, cyclohexyl group, benzyl group, hydroxymethyl group, alkoxymethyl group, phenyl group, 2,4,5-tetramethylphenyl group, 4-chlorophenyl group, trimethylsilyl, etc.);

Methacrylamides, specifically, methacrylamide, N-monosubstituted methacrylamide, N-disubstituted methacrylamide (substituents are aliphatic, aromatic and silyl groups; for example, methyl, Ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, tert-octyl group, cyclohexyl group, benzyl group, hydroxymethyl group, alkoxymethyl group,
Phenyl group, 2,4,5-tetramethylphenyl group, 4
-Chlorophenyl group, trimethylsilyl, etc.);

Olefins, specifically, styrenes such as dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene; For example, styrene, methyl styrene,
Dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinyl benzoate, etc .;

Vinyl ethers, specifically, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and the like; other monomers such as butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, Dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N-vinyl oxazolidone, N-vinyl pyrrolidone, vinylidene chloride, methylene malononitrile, Vinylidene, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate,
Examples include dibutyl-2-acryloyloxyethyl phosphate, dioctyl-2-methacryloyloxyethyl phosphate, and the like.

The terminal dissociable vinyl polymer may be a homopolymer obtained by polymerizing one type of vinyl monomer alone or a copolymer obtained by copolymerizing two or more types of vinyl monomers. The vinyl monomer is selected according to various purposes (for example, Tg control, solubility improvement, dispersion stability).

The content of the dissociable group in the terminal dissociable vinyl polymer is preferably from 0.1 to 2.0 mmol / g, more preferably from 0.15 to 1.5 mmol / g. It is particularly preferably 0.2 to 1.0 mmol / g. In the terminal dissociable vinyl polymer, the dissociating group may form a salt with an alkali metal ion (for example, Na ⁺ , K ^+, etc.) or an ammonium ion.

Molecular weight of the terminal dissociable vinyl polymer
(Mw) is preferably from 1,000 to 100,000, more preferably from 2,000 to 20,000,
More preferably, it is from 3000 to 15000, and 30
It is particularly preferably from 00 to 10,000. When the molecular weight is less than 1000, it tends to be difficult to obtain a stable dispersion, and when the molecular weight is more than 100,000, the solubility in an organic solvent becomes poor, or even if dissolved, the viscosity of the solution increases. This is not preferred because the dispersion tends to be difficult.

Specific examples (P-1) to 120)) of the terminal dissociable vinyl polymer are listed below. The terminal dissociable vinyl polymer used in the present invention is not limited to these specific examples. Specific Examples P-1) Methyl methacrylate-butyl acrylate copolymer using mercaptoacetic acid as a chain transfer agent P-2) Methyl methacrylate-methyl acrylate copolymer using mercaptoacetic acid as a chain transfer agent P-3) Chain transfer Butyl acrylate-styrene copolymer using mercaptoacetic acid as an agent P-4) Polyethyl methacrylate using mercaptoacetic acid as a chain transfer agent P-5) Polyn using mercaptoacetic acid as a chain transfer agent
-Butyl methacrylate P-6) polyisobutyl methacrylate using mercaptoacetic acid as a chain transfer agent P-7) polyisopropyl methacrylate using mercaptoacetic acid as a chain transfer agent P-8) polydimethyl using mercaptoacetic acid as a chain transfer agent Acrylamide P-9) Poly (2-tert-butylphenyl acrylate) using mercaptoacetic acid as a chain transfer agent P-10) Poly (4-tert-butylphenyl acrylate) using mercaptoacetic acid as a chain transfer agent

P-11) n-Butyl methacrylate-N-vinyl-2- using mercaptoacetic acid as a chain transfer agent
Pyrrolidone copolymer P-12) Polydibutyl acrylamide using mercaptoacetic acid as a chain transfer agent P-13) Polytert-butyl methacrylate using mercaptoacetic acid as a chain transfer agent P-14) Mercaptoacetic acid used as a chain transfer agent Isobutyl methacrylate-butyl acrylate copolymer P-15) poly-2,4,5-trimethylphenylacrylamide using mercaptoacetic acid as a chain transfer agent P-16) polyphenylacrylamide P- using mercaptoacetic acid as a chain transfer agent 17) Polytetrahydrofurfuryl acrylate using mercaptoacetic acid as a chain transfer agent P-18) Butyl methacrylate-tetrahydrofurfuryl acrylate copolymer using mercaptoacetic acid as a chain transfer agent P-19) Mercaptoacetic acid as a chain transfer agent Use Diacetone acrylamide-methyl methacrylate copolymer P-20) Ethyl methacrylate-n-butyl acrylate copolymer using mercaptoacetic acid as a chain transfer agent

P-21) Methyl methacrylate-cyclohexyl acrylate copolymer using mercaptoacetic acid as a chain transfer agent P-22) Poly n-butyl acrylate using mercaptoacetic acid as a chain transfer agent P-23) As a chain transfer agent N- using mercaptoacetic acid
Butyl acrylate-butyl methacrylate copolymer P-24) Polysec-butyl methacrylate using mercaptoacetic acid as a chain transfer agent P-25) Polysec-butyl acrylate using mercaptoacetic acid as a chain transfer agent P-26) Chain transfer N-mercaptoacetic acid
Butyl acrylate-pentyl methacrylate copolymer P-27) Ethyl acrylate-cyanoethyl acrylate copolymer using mercaptoacetic acid as a chain transfer agent P-28) Polydiphenylacrylamide using mercaptoacetic acid as a chain transfer agent P-29) Chain N- using mercaptoacetic acid as a transfer agent
Butyl methacrylate-2-hydroxyethyl methacrylate copolymer P-30) Cyanoethyl acrylate-benzyl methacrylate copolymer using mercaptoacetic acid as a chain transfer agent

P-31) Isobutyl methacrylate-tetrahydrofurfuryl acrylate copolymer using mercaptoacetic acid as a chain transfer agent P-32) n-type using mercaptoacetic acid as a chain transfer agent
Butyl methacrylate-tert-butylacrylamide copolymer P-33) n- using mercaptoacetic acid as a chain transfer agent
Butyl methacrylate-1H, 1H, 2H, 2H-perfluorodecyl acrylate copolymer P-34) n- using mercaptoacetic acid as a chain transfer agent
Butyl methacrylate-phenylacrylamide copolymer P-35) 2-mercaptoacetic acid using a chain transfer agent
Ethylhexyl methacrylate-methyl acrylate copolymer P-36) Poly-3-methoxybutyl methacrylate using mercaptoacetic acid as a chain transfer agent P-37) Cyclohexyl methacrylate-allyl methacrylate copolymer P- using mercaptoacetic acid as a chain transfer agent 38) Isopropyl methacrylate-furfuryl methacrylate copolymer using mercaptoacetic acid as a chain transfer agent P-39) Poly-2-butoxyethyl methacrylate using mercaptoacetic acid as a chain transfer agent P-40) Mercaptoacetic acid as a chain transfer agent Ethyl acrylate-phenyl methacrylate-copolymer used (72:15:13)

P-41) Isobutyl methacrylate-2- (2-ethoxyethoxy) ethyl methacrylate copolymer using mercaptoacetic acid as a chain transfer agent P-42) Isobutyl methacrylate-polyethylene glycol using mercaptoacetic acid as a chain transfer agent Methacrylic acid ester copolymer of monomethyl ether (ethyleneoxy chain repeating number 23) P-43) Isobutyl methacrylate-dipropylene glycol monomethacrylate copolymer using mercaptoacetic acid as a chain transfer agent P-44) Mercapto as a chain transfer agent Methacrylic acid ester copolymer of isobutyl methacrylate-polyethylene glycol monomethyl ether (ethyleneoxy chain repetition number: 45) using acetic acid P-45) Isobutylamine using mercaptoacetic acid as a chain transfer agent Relate-tetrahydrofurfuryl methacrylate copolymer P-46) Isobutyl acrylate-methoxystyrene copolymer using mercaptoacetic acid as a chain transfer agent P-47) Isobutyl acrylate-N-vinylpyrrolidone using mercaptoacetic acid as a chain transfer agent Copolymer P-48) Methyl methacrylate-butyl acrylate copolymer using 2-mercaptosuccinic acid as a chain transfer agent P-49) Methyl methacrylate-methyl acrylate copolymer using 2-mercaptosuccinic acid as a chain transfer agent Combined P-50) Butyl acrylate-styrene copolymer using 2-mercaptosuccinic acid as a chain transfer agent

P-51) Polyethyl methacrylate using 2-mercaptosuccinic acid as a chain transfer agent P-52) Poly-n-butyl methacrylate using 2-mercaptosuccinic acid as a chain transfer agent P-53) Chain transfer agent Polyisobutyl methacrylate using 2-mercaptosuccinic acid P-54) Polyisopropyl methacrylate using 2-mercaptosuccinic acid as a chain transfer agent P-55) Polydimethylacrylamide using 2-mercaptosuccinic acid as a chain transfer agent P-56) Poly (2-tert-butylphenyl acrylate) using 2-mercaptosuccinic acid as a chain transfer agent P-57) Poly (4-tert-butylphenyl) using 2-mercaptosuccinic acid as a chain transfer agent Acrylate) P-58) Using 2-mercaptosuccinic acid as a chain transfer agent N-butyl methacrylate-tetrahydrofurfuryl acrylate copolymer P-59) Polydibutylacrylamide using 2-mercaptosuccinic acid as a chain transfer agent P-60) Dibutylacrylamide using 2-mercaptosuccinic acid as a chain transfer agent -Isobutyl methacrylate copolymer

P-61) Isobutyl methacrylate-butyl acrylate copolymer using 2-mercaptosuccinic acid as a chain transfer agent P-62) Poly 2,4,5- using 2-mercaptosuccinic acid as a chain transfer agent Trimethylphenylacrylamide P-63) Polyphenylacrylamide using 2-mercaptosuccinic acid as a chain transfer agent P-64) Polytetrahydrofurfuryl acrylate using 2-mercaptosuccinic acid as a chain transfer agent P-65) Chain transfer agent Isobutyl methacrylate-tetrahydrofurfuryl acrylate copolymer using 2-mercaptosuccinic acid P-66) diacetone acrylamide-methyl methacrylate copolymer using 2-mercaptosuccinic acid as a chain transfer agent P-67) Chain transfer 2-mercaptosuccinic acid Ethyl methacrylate-n-butyl acrylate copolymer P-68) Methyl methacrylate-cyclohexyl acrylate copolymer using 2-mercaptosuccinic acid as a chain transfer agent P-69) Using 2-mercaptosuccinic acid as a chain transfer agent Polybutyl acrylate P-70) n-butyl acrylate-butyl methacrylate copolymer using 2-mercaptosuccinic acid as a chain transfer agent

P-71) Polysec-butyl methacrylate using 2-mercaptosuccinic acid as a chain transfer agent P-72) Polysec-butyl acrylate using 2-mercaptosuccinic acid as a chain transfer agent P-73) Chain Polytetrahydrofurfuryl methacrylate using 2-mercaptosuccinic acid as a transfer agent P-74) Polydiphenylacrylamide using 2-mercaptosuccinic acid as a chain transfer agent P-75) Using 2-mercaptosuccinic acid as a chain transfer agent P-76) butyl methacrylate-2-hydroxyethyl methacrylate copolymer using 2-mercaptosuccinic acid as a chain transfer agent P-77) cyanoethyl acrylate using 2-mercaptosuccinic acid as a chain transfer agent Benzyl methacrylate copolymer P 78) n-Butyl methacrylate-tetrahydrofurfuryl acrylate copolymer using 2-mercaptosuccinic acid as a chain transfer agent P-79) n-butyl methacrylate-tert-butyl using 2-mercaptosuccinic acid as a chain transfer agent Acrylamide copolymer P-80) n-butyl methacrylate-1H, 1H, 2H, 2 using 2-mercaptosuccinic acid as a chain transfer agent
H-perfluorodecyl acrylate copolymer

P-81) n-butyl methacrylate-phenylacrylamide copolymer using 2-mercaptosuccinic acid as a chain transfer agent P-82) 2-ethylhexyl methacrylate using 2-mercaptosuccinic acid as a chain transfer agent Methyl acrylate copolymer P-83) Poly-3-methoxybutyl methacrylate using 2-mercaptosuccinic acid as a chain transfer agent P-84) Cyclohexyl methacrylate-allyl methacrylate copolymer using 2-mercaptosuccinic acid as a chain transfer agent Combined P-85) Isopropyl methacrylate-furfuryl methacrylate copolymer using 2-mercaptosuccinic acid as a chain transfer agent P-86) Poly-2-butoxyethyl methacrylate P- using 2-mercaptosuccinic acid as a chain transfer agent 87) The chain transfer agent Isobutyl methacrylate-2- (2-ethoxyethoxy) ethyl methacrylate copolymer using rucaptosuccinic acid P-88) isobutyl methacrylate-polyethylene glycol monomethyl ether using 2-mercaptosuccinic acid as a chain transfer agent (number of repeating ethylene oxy chains) 2
3) Methacrylic acid ester copolymer P-89) Isobutyl methacrylate-dipropylene glycol monomethacrylate copolymer using 2-mercaptosuccinic acid as a chain transfer agent P-90) 2-mercaptosuccinic acid as a chain transfer agent Methacrylic acid ester copolymer of isobutyl methacrylate-polyethylene glycol monomethyl ether (ethyleneoxy chain repeating number 9) used

P-91) Poly n-butyl methacrylate using 2-mercaptopropionic acid as a chain transfer agent P-92) Poly 2,4,5-trimethylphenylacrylamide using 2-mercaptopropionic acid as a chain transfer agent P-93) Polyphenylacrylamide using 2-mercaptopropionic acid as a chain transfer agent P-94) Polytetrahydrofurfuryl acrylate using 2-mercaptopropionic acid as a chain transfer agent P-95) 4- Poly (n-butyl methacrylate P-96 using (2-mercaptoethyloxy) benzoic acid) Polyphenylacrylamide using 4- (2-mercaptoethyloxy) benzoic acid as a chain transfer agent P-97) As a chain transfer agent Methyl methacrylate using sodium 2-mercaptoethanesulfonate -Butyl acrylate copolymer P-98) Poly-n-butyl methacrylate using 2-mercaptoethanesulfonic acid sodium as a chain transfer agent P-99) Polyisobutyl methacrylate using 2-mercaptoethanesulfonic acid sodium as a chain transfer agent P-100) Polyisopropyl methacrylate using sodium 2-mercaptoethanesulfonate as a chain transfer agent

P-101) Polydibutyl acrylamide using sodium 2-mercaptoethanesulfonate as a chain transfer agent P-102) Polyphenyl acrylate using sodium 2-mercaptoethanesulfonate as a chain transfer agent P-103) Chain Polytetrahydrofurfuryl acrylate using sodium 2-mercaptoethanesulfonate as a transfer agent P-104) Isobutyl methacrylate-butyl acrylate copolymer using sodium 2-mercaptoethanesulfonate as a transfer agent P-105) Chain transfer 2,4-trimethylphenylacrylamide using 2-mercaptoethanesulfonic acid sodium as the agent P-106) Polyphenylacrylamide using 2-mercaptoethanesulfonic acid sodium as the chain transfer agent P-107) Chain transfer agent 2- Ethyl methacrylate-n-butyl acrylate copolymer using sodium rucaptoethanesulfonic acid P-108) Phenylacrylamide-n-butyl acrylate copolymer using 2-mercaptoethanesulfonic acid sodium as a chain transfer agent P-109 ) Poly-n-butyl methacrylate using 2-mercaptopropanesulfonic acid as a chain transfer agent P-110) Polyisobutyl methacrylate using 2-mercaptopropanesulfonic acid as a chain transfer agent

P-111) Polyisopropyl methacrylate using 2-mercaptopropanesulfonic acid as a chain transfer agent P-112) Polydibutylacrylamide using 2-mercaptopropanesulfonic acid as a chain transfer agent P-113) Chain transfer agent P-114) Polytetrahydrofurfuryl acrylate using 2-mercaptopropanesulfonic acid as a chain transfer agent P-115) 2,3-Dimercapto-1 as a chain transfer agent −
Polybutyl methacrylate using propanesulfonic acid P-116) 2,3-dimercapto-1-
Polyphenyl acrylate using propane sulfonic acid P-117) 2,3-dimercapto-1-
Polytetrahydrofurfuryl acrylate using propanesulfonic acid P-118) 2,3-dimercapto-1-
Polyisobutyl methacrylate using propane sulfonic acid P-119) 2,3-dimercapto-1-
Tert-octylacrylamide-n-butyl acrylate copolymer using propanesulfonic acid P-120) 2,3-dimercapto-1- as a chain transfer agent
Polyisobutyl acrylate using propanesulfonic acid

Next, an example of a method for producing a terminal dissociable vinyl polymer will be described. The present invention is not limited to this production example at all. In the following, “parts” indicates “parts by mass”. <Production Example> n-butyl methacrylate 142.2 parts,
A mixed solution (A) consisting of 80 parts of tetrahydrofuran and 0.15 parts of 2,2'-azobis (2,4-dimethylvaleronitrile), and a mixed solution (B) consisting of 5.07 parts of mercaptoacetic acid and 40 parts of tetrahydrofuran Was prepared. Next, 20 parts of tetrahydrofuran, 2,2 ′
-Azobis (2,4-dimethylvaleronitrile)
02 parts were charged into a flask, and the temperature was raised to 65 ° C. while stirring under a nitrogen seal, and then the mixed liquids (A) and (B) were simultaneously added dropwise over 2 hours. After completion of the dropwise addition, 0.02 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was further reacted at the same temperature for 5 hours. The obtained polymer solution was concentrated under reduced pressure to obtain 125 parts of the desired terminally dissociable vinyl polymer P-5. The content of the dissociable group determined by titration was 0.44 mmol / g.

-Production of Dispersion of Colored Fine Particles- The dispersion of colored fine particles of the present invention is obtained by dispersing colored fine particles containing the oil-soluble dye and the terminal-dissociable vinyl polymer in an aqueous medium (aqueous liquid containing at least water). It is manufactured by doing. Specifically, for example, a method of preparing a dispersion of the terminal dissociable vinyl polymer in advance and impregnating the dispersion with the oil-soluble dye, or a method of co-emulsification dispersion is used. Among these, the co-emulsification dispersion method is preferable. As the co-emulsification dispersion method, water is added to an organic solvent phase containing the terminal dissociable vinyl polymer and the oil-soluble dye, and the organic solvent is dissolved in water. A method of emulsifying the organic solvent phase to form fine particles by either adding a solvent phase is preferred.

Here, a method for preparing a dispersion of the terminal-dissociable vinyl polymer and impregnating the dispersion with the oil-soluble dye will be described. A first example of this method includes a first step of preparing the vinyl polymer dispersion, a second step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, A third step of preparing a colored fine particle dispersion by mixing with a polymer dispersion.
A second example of this method is a first step of preparing the vinyl polymer dispersion, and preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, and converting the dye solution and a liquid containing at least water. A second step of mixing to prepare a dye fine particle dispersion; and a third step of mixing the vinyl polymer dispersion and the dye fine particle dispersion to prepare a colored fine particle dispersion.

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

In the colored fine particle dispersion, the amount of the terminal dissociable vinyl polymer used is preferably from 10 to 1,000 parts by mass, more preferably from 20 to 400 parts by mass, per 100 parts by mass of the oil-soluble dye. When the amount of the terminal dissociable vinyl polymer used is less than 10 parts by mass, fine and stable dispersion tends to be difficult, and 100
If the amount exceeds 0 parts by mass, the proportion of the oil-soluble dye in the colored fine particle dispersion becomes small, and when the colored fine particle dispersion is used as an aqueous ink, there is a tendency that there is no room for formulation design.

In the colored fine particles, it is preferable that the oil-soluble dye is dispersed in the terminal dissociable vinyl polymer. The content of the colored fine particles in the colored fine particle dispersion is preferably from 1 to 45% by mass,
30 mass% is more preferable. The content can be appropriately adjusted by dilution, evaporation, ultrafiltration, or the like. The average particle size of the colored fine particles is preferably 1 to 500 nm, more preferably 3 to 300 nm, and 3 to 100 nm.
Is particularly preferred. The average particle size can be adjusted by centrifugation, filtration, or the like.

-Organic Solvent- The organic solvent used for producing the colored fine particle dispersion is not particularly limited, and may be appropriately selected based on the solubility of the oil-soluble dye or the terminal dissociable vinyl polymer. For example, ketone solvents such as acetone, methyl ethyl ketone and diethyl ketone; alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol and tert-butanol; and chlorine solvents such as chloroform and methylene chloride. ,benzene,
Aromatic solvents such as toluene, ethyl acetate, butyl acetate,
Ester solvents such as isopropyl acetate; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; glycol ether solvents such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent used is not particularly limited as long as the effect of the present invention is not impaired, but is preferably from 10 to 100 parts by mass of the terminal dissociable vinyl polymer.
2000 parts by mass is preferable, and 100 to 1000 parts by mass is more preferable. When the amount of the organic solvent is less than 10 parts by mass, the 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 is removed for removing the organic solvent. Concentration process becomes essential,
In addition, there is a tendency that there is no room for mixing 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 to 100 ° C. under normal pressure to reduced pressure, and is preferably performed at 40 to 100 ° C. under normal pressure or 10 to 50 ° C. under reduced pressure.

—Additives— The colored fine particle dispersion of the present invention may contain additives appropriately selected according to the purpose within a range that does not impair the effects of the present invention. Examples of the additive include a neutralizer, a high-boiling organic solvent, a dispersant, and a dispersion stabilizer.

When the terminal dissociable vinyl polymer has an unneutralized dissociable group, the neutralizing agent is suitable for adjusting the pH of the colored fine particle dispersion, adjusting the self-emulsifying property, imparting dispersion stability, and the like. Can be used for Examples of the neutralizing agent include an organic base and an inorganic alkali.

Examples of the organic base include triethanolamine, diethanolamine, N-methyldiethanolamine, dimethylethanolamine and the like. Examples of the inorganic alkali include hydroxides of alkali metals (eg, sodium hydroxide, lithium hydroxide, potassium hydroxide, etc.), carbonates (eg, sodium carbonate, sodium hydrogen carbonate, etc.), and ammonia. From the viewpoint of improving the dispersion stability of the colored fine particle dispersion, the neutralizing agent is preferably added so as to have a pH of 4.5 to 10.0, and added so as to have a pH of 6.0 to 10.0. Is more preferred.

The high-boiling organic solvent is used for adjusting the viscosity, specific gravity, and printing performance of the colored fine particle dispersion. The high-boiling organic solvent preferably has a boiling point of 150 ° C or higher, more preferably 170 ° C or higher. The high-boiling organic solvent preferably has a dielectric constant of 3 to 12, more preferably 4 to 10.
Here, the dielectric constant means a relative dielectric constant with respect to vacuum at 25 ° C. As the high boiling organic solvent, compounds described in U.S. Pat. No. 2,322,027 can be used. Specifically, phosphoric acid triesters,
Examples include phthalic acid diesters, alkylnaphthalenes, and benzoic acid esters. These can be liquid or solid at room temperature depending on the purpose. The amount of the high boiling solvent used is not particularly limited as long as the effect of the present invention is not impaired, but it is preferably 0 to 1000 parts by mass relative to 100 parts by mass of the terminal dissociable vinyl polymer. 300 parts by mass is more preferred.

The above-mentioned dispersant and / or dispersion stabilizer is
The terminal dissociable vinyl polymer dispersion, the terminal dissociable vinyl polymer solution, the dye solution, a solution containing at least water, and the like may be added to the dispersion. In the pre-preparation step, the terminal dissociable vinyl polymer, dye solution,
It is preferably added to a solution containing water. Examples of the dispersant and dispersion stabilizer include various cationic, anionic and nonionic surfactants, water-soluble or water-dispersible low molecular weight compounds, oligomers and the like. The addition amount of the dispersant and the dispersion stabilizer is 0 to 100% by mass, and preferably 0 to 20% by mass, based on the total of the oil-soluble dye and the terminal dissociable vinyl polymer.

Although the colored fine particle dispersion of the present invention can be used in various fields, it is suitable for aqueous inks for writing, aqueous printing inks, information recording inks and the like. It can be used particularly preferably.

(Ink for Inkjet Recording and Inkjet Recording Method) The ink for inkjet recording of the present invention contains the colored fine particle dispersion of the present invention.
Further, it contains other components appropriately selected as needed. In the inkjet recording method of the present invention, recording is performed using the inkjet recording ink,
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.

-Other Components- The other components are contained within a range that does not impair the effects of the present invention. 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. Stabilizer, rust inhibitor, chelating agent,
And other known additives.

The above-mentioned anti-drying agent is suitably used for the purpose of preventing clogging due to drying of the ink for ink-jet recording at the ink ejection port of a nozzle used in the ink-jet recording method.

As the anti-drying agent, a water-soluble organic solvent having a lower vapor pressure than water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, and the like.
Polyhydric alcohols represented by dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, trimethylolpropane, etc., ethylene glycol monomethyl (or ethyl) Lower alkyl ethers of polyhydric alcohols such as ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2- Heterocycles such as imidazolidinone and N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3-
Sulfur-containing compounds such as sulfolene, diacetone alcohol,
Examples include polyfunctional compounds such as diethanolamine and urea derivatives. Among these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable. These anti-drying agents may be used alone or in combination of two or more. The content of the anti-drying agent in the ink for inkjet recording is preferably from 10 to 50% by mass.

The penetration enhancer is preferably used for the purpose of better penetrating the ink for ink jet recording into paper.

Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether and 1,2-hexanediol, sodium lauryl sulfate, and the like.
Examples include sodium oleate and nonionic surfactants. The permeation enhancer is contained within a range that does not cause bleeding of print, paper dropout (print-through), and the like, and usually exhibits a sufficient effect when contained in the ink for inkjet recording at about 5 to 30% by mass.

The ultraviolet absorber is used for the purpose of improving the storability of an image. As the ultraviolet absorber,
For example, JP-A-58-185677 and JP-A-61-1
90537, JP-A-2-782, 5-1
Benzotriazole compounds described in JP-A-97075 and JP-A-9-34057, and JP-A-46-278.
No. 4, JP-A-5-194483, benzophenone-based compounds described in U.S. Pat. No. 3,214,463, JP-B-48-30492, JP-B-56-2114.
No. 1, cinnamic acid-based compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, The triazine compounds described in JP-T-8-501291 and the like, Research Disclosure No. Compounds described in No. 24239 and compounds emitting fluorescent light by absorbing ultraviolet rays, represented by stilbene-based and benzoxazole-based compounds, so-called fluorescent whitening agents, and the like.

The antioxidant is used for the purpose of improving the storability of an image. As the antioxidant, for example, various organic and metal complex antifading agents can be used. As the organic anti-fading agent,
Hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines,
And heterocycles. Examples of the metal complex-based anti-fading agent include a nickel complex, a zinc complex, and the like. 1
No. 7643, Nos. VII I-J; 15162; No. 18716, left column, page 650; 36544
No. 527, ibid. Page 872 of 307105, N
o. Compounds described in the patent cited in U.S. Pat. No. 15,162, and pages 127 to 13 of JP-A-62-215272.
The compounds included in the general formulas and the compound examples of the representative compounds described on page 7 can be used.

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

As the pH adjusting agent, the neutralizing agent (organic base, inorganic alkali) can be used. The p
For the purpose of improving the storage stability of the inkjet recording ink, the H adjuster is preferably added so that the inkjet recording ink has a pH of 6 to 10.
It is more preferable to add H7 to H10.

As the surface tension adjusting agent, nonionic,
Cationic or anionic surfactants are included. The surface tension of the inkjet recording ink of the present invention is preferably from 25 to 70 mPa · s, and is preferably from 25 to 60 mPa · s.
mPa · s is more preferred. Further, the viscosity of the inkjet recording ink of the present invention is preferably 30 mPa · s or less, more preferably 20 mPa · s or less.

As the defoaming agent, a fluorine-based or silicone-based compound, a chelating agent represented by EDTA, or the like can be used as required.

The ink-jet recording ink of the present invention comprises:
Printing can be suitably performed on a known recording material. For example, plain paper, resin-coated paper, inkjet paper, film, electrophotographic paper, fabric, glass, metal, ceramic, and the like can be used. The recording material is not particularly limited, but is preferably ink jet paper. Examples of the inkjet paper include, for example, JP-A-8-16917.
No. 2, No. 8-27693, No. 2-27667
Nos. 0, 7-276789 and 9-3234.
No. 75, JP-A-62-238873, JP-A-10-153899, JP-A-10-217473, JP-A-10-235995, and JP-A-10-33794.
No. 7, No. 10-217597, No. 10-33
No. 7947, and the like.

In the present invention, the following recording paper and recording film are preferably used as the recording material in addition to the ink jet paper. The recording paper and recording film are formed by laminating a support and an ink receiving layer, and if necessary, laminating other layers such as a back coat layer. In addition, each layer including the ink receiving layer may be a single layer, or may be two or more layers.

As the support, LBKP, NBKP
Chemical pulp, GP, PGW, RMP, TMP, CT
Examples thereof include mechanical pulp such as MP, CMP, and CGP, and waste paper pulp such as DIP. In the pulp,
If necessary, conventionally known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers and the like may be added and mixed. The support can be formed by using various apparatuses such as a fourdrinier paper machine and a round paper machine. The support may further be a synthetic paper, a plastic film sheet or the like.

The thickness of the support is 10 to 250.
It is about μm, and the basis weight is desirably 10 to 250 g / m 2.

On the support, the ink receiving layer and the back coat layer selected as necessary may be directly laminated, or a size press or an anchor coat layer may be provided with starch, polyvinyl alcohol or the like. After that, the ink receiving layer and the 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 supports, both surfaces are polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof).
Paper and a plastic film are preferred, and a white pigment (eg, titanium oxide, zinc oxide) or a tinting dye (eg, cobalt blue, ultramarine, neodymium oxide) is more preferably added to the polyolefin. preferable.

The ink receiving layer contains a pigment, an aqueous binder, a mordant, a waterproofing agent, a lightfastness improving agent, a surfactant, and other additives.

The pigment is preferably a white pigment.
Examples of the white pigment include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate,
Inorganic white pigments such as aluminum hydroxide, alumina, lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, zinc carbonate, and organic pigments such as styrene pigment, acrylic pigment, urea resin, melamine resin, etc. No. Among these, porous inorganic pigments are preferred, and synthetic amorphous silica having a large pore area is particularly preferred. As the synthetic amorphous silica, either silicic anhydride obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but hydrous silicic acid is particularly preferable.

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. And water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion. These may be used alone or in combination of two or more. Among these, adhesion to the pigment,
In view of the peel resistance of the ink receiving layer, polyvinyl alcohol and silanol-modified polyvinyl alcohol are preferred.

The mordant is preferably immobilized, and for that purpose, a polymer mordant is preferred. Examples of the polymer mordant include JP-A-48-283.
No. 25, No. 54-74430, No. 54-124726
No. 55-22766, No. 55-142339,
No. 60-23850, No. 60-23851, No. 60
-23852, 60-23853, 60-57
No. 836, No. 60-60643, No. 60-11883
No. 4, No. 60-122940, No. 60-122941
No. 60-122942, No. 60-235134
JP-A-1-161236, U.S. Pat.
No. 84430, No. 2548564, No. 3148061
Nos. 3309690, 4115124, 41
24386, 4193800, 4273753
Nos. 4,282,305 and 4,450,224. JP-A-1-161236, 21
Polymer mordants described on pages 2 to 215 are preferred. The use of these polymer mordants is preferable in that an image having excellent image quality is obtained and the light fastness of the image is improved.

The waterproofing agent is used for the purpose of making an image waterproof. As the water-proofing agent, a cationic resin is preferable. Examples of the cationic resin include polyamide polyamine epichlorohydrin, polyethylene imine, polyamine sulfone, dimethyl diallyl ammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferred. The content of the cationic resin is preferably from 1 to 15% by mass, more preferably from 3 to 10% by mass, based on the total solid content of the ink receiving layer.

Examples of the light resistance improver include zinc sulfate, zinc oxide, hinderamine antioxidants, and benzotriazole-based 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. Examples of the surfactant include JP-A-62-17346.
No. 3, No. 62-183457. Note that 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, tetrafluoroethylene resin). No. (columns 8-17), JP-A-61-
JP-A Nos. 20994 and 62-135826.

Examples of the other additives include a pigment dispersant, a thickener, a defoamer, a dye, a fluorescent brightener, a preservative, a pH adjuster, a matting agent, and a hardener. .

The back coat layer contains a white pigment, an aqueous binder and other components.

Examples of the white pigment include light calcium carbonate, heavy calcium carbonate, kaolin, talc,
Calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo boehmite, hydroxylated White inorganic pigments such as aluminum, 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. No.

As the aqueous binder, styrene /
Water-soluble polymers such as maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, and styrene Water-dispersible polymers such as butadiene latex and acrylic emulsion, and the like.

Examples of the other components include an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, and a waterproofing agent.

Incidentally, a polymer latex may be added to each layer of the recording paper and recording film. 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. As the polymer latex,
JP-A-62-245258 and JP-A-62-136648.
And Nos. 62-110066. Low glass transition temperature (below 40 ° C)
When the polymer latex is added to the layer containing the 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, curling can be prevented.

The ink jet recording ink of the present invention comprises
It can be applied to any ink jet recording method, for example, a charge control method in which ink is ejected using electrostatic attraction, a drop-on-demand method (pressure pulse method) using vibration pressure of a piezo element, and an acoustic beam as an electric signal. Acoustic ink-jet method that irradiates ink and discharges ink using radiation pressure, thermal ink-jet (bubble jet (registered trademark)) method that heats ink to form bubbles, and uses the generated pressure, etc. It is preferably 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 is included.

[0159]

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. <Production Example 1 (Preparation of colored fine particle dispersion (B-1))> 4 parts of isopropyl alcohol, tert-butanol
6 parts, a terminal dissociable vinyl polymer (P-5 (acid content: 0.
44 mmol / g)) In a mixture of 1.2 parts and 0.8 part of the oil-soluble dye (D-1), 2 mol / L sodium hydroxide was added in an amount sufficient to neutralize the acid of the terminal dissociable vinyl polymer. After the addition, the temperature was raised to 80 ° C. Thereafter, 30 parts of water was added while stirring. This liquid was concentrated at 40 ° C. under reduced pressure to prepare a colored fine particle dispersion having a solid content of 15%. The particle size of the colored fine particles in the colored fine particle dispersion was 23 nm in volume average diameter (Microtrac UPA150; measured by Nikkiso Co., Ltd.). Hereinafter, this is abbreviated as colored fine particle dispersion (B-1).

<Production Example 2 (Colored fine particle dispersion (B-2))
Preparation> Ethyl acetate 3 parts, cyclohexanone 0.
5 parts, a terminal dissociable vinyl polymer (P-7 (acid content: 0.
38 mmol / g)) 1.0 part, oil-soluble dye (D-
3) A mixture of 1.0 part was prepared. On the other hand, a mixture of 2 mol / L sodium hydroxide, 15 parts of water, and 0.2 parts of sodium di (2-ethylhexyl) sulfosuccinate was prepared in such an amount that the acid of the terminal dissociable vinyl polymer was neutralized. The two liquid mixtures were combined, mixed and emulsified with a homogenizer, and then concentrated at 40 ° C. under reduced pressure to obtain a solid content of 1%.
A 2% dispersion of colored fine particles was prepared. The particle diameter of the colored fine particles in the colored fine particle dispersion was 25 nm in volume average diameter. Hereinafter, this is abbreviated as colored fine particle dispersion (B-2).

<Production Example 3 (Colored fine particle dispersion (B-3))
Preparation> Tetrahydrofuran 5 parts, tert-butanol 5 parts, terminal-dissociable vinyl polymer (P-99
(Acid content 0.24 mmol / g)) A mixture of 0.6 part and 1.4 parts of an oil-soluble dye (D-4) was heated to 80 ° C, and then 30 parts of water was added with stirring. Was added.
This liquid was concentrated at 40 ° C. under reduced pressure to prepare a colored fine particle dispersion having a solid content of 8.6%. The particle diameter of the colored fine particles in the colored fine particle dispersion was 19 nm in volume average diameter. Less than,
This is abbreviated as colored fine particle dispersion (B-3).

<Production Examples 4 to 12> In a similar manner to that of Production Example 1, B-4 to B-7 and Production Examples B-11 to B-12 were used.
Was prepared in the same manner as in Production Example 2, and B-10 was produced in the same manner as in Production Example 3. Table 1 shows the terminally dissociable vinyl polymer and the oil-soluble dye used. The polymers used in Production Examples B-11 and B-12 were as follows, and were non-terminal dissociable vinyl polymers. PH-1: n-butyl methacrylate-acrylic acid (9
5: 5) Copolymer PH-2: Methyl methacrylate-n-butyl acrylate-acrylic acid (60: 30: 5) copolymer

[0163]

[Table 1]

Example 1 42 parts of the colored fine particle dispersion (B-1) prepared in Production Example 1 were mixed with 8 parts of diethylene glycol, 8 parts of glycerin, 5 parts of triethylene glycol monobutyl ether, and hexaethylene glycol monododecyl sulfate. 0.5 parts of sodium ether, sodium di (2-ethylhexyl) sulfosuccinate
0.5 part and 36 parts of ion-exchanged water are mixed,
The mixture was filtered through a 45 μm filter to prepare an aqueous inkjet recording ink.

(Examples 2 to 10) In Example 1, the colored fine particle dispersion (B-1) was replaced with Production Example 2
To (B-2) to (B-).
Ink jet recording inks of Examples 2 to 10 were respectively prepared in the same manner as in Example 1 except that each was changed to 10).

(Comparative Examples 1 and 2)
The colored fine particle dispersion (B-1) was prepared according to any one of Production Examples 11 to 11.
Ink jet recording inks of Comparative Examples 1 and 2 were prepared in the same manner as in Example 1 except that the colored fine particle dispersions (B-11) and (B-12) prepared in Example 12 were respectively used.

(Image Recording and Evaluation) The ink-jet recording inks of the respective Examples and Comparative Examples were evaluated as follows. The results are shown in Table 2. still,
In Table 2, "color tone", "paper dependence", "waterfastness" and "lightfastness" refer to each ink jet recording ink.
Inkjet printer (manufactured by EPSON Corporation; P
M-700C) and photo glossy paper (Fuji Photo Film Co., Ltd .; inkjet paper, photo grade)
Is a result of the evaluation based on the following criteria after recording an image on the image.

<Color Tone> The recorded image was observed and judged "good" or "poor", and evaluated 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 (poor) 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> Xenon light (85000 lx) was irradiated on the photo glossy paper on which the image was formed using a weather meter (Atlas CI65) for 3 days, and the image density before and after the xenon irradiation was measured using a reflection densitometer. (X-Rite31
0TR) and evaluated as the residual dye ratio.
The reflection density was measured at three points of 1, 1.5 and 2.0. In any of the concentrations, the case where the residual dye ratio was 70% or more was evaluated as A, and B was evaluated when one or two points were less than 70%, and C was evaluated when it was less than 70% at all concentrations.

[0172]

[Table 2]

As is evident from the results in Table 2, the ink jet recording inks of the examples have a small particle size, excellent printability, excellent color development and color tone, are not dependent on paper, and have water resistance and light resistance. Was excellent.

[0174]

According to the present invention, when printing is performed using a nozzle or the like, clogging does not occur at the nozzle tip, there is no dependence on paper, and color formation when printing is performed on arbitrarily selected paper. It is possible to provide an ink jet recording ink and an ink jet recording method which are excellent in properties and color tone and also excellent in water resistance and light resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 67/46 C09B 67/46 Z C09D 11/00 C09D 11/00 B41J 3/04 101Y (72) Inventor Kazue Sano 210 Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F term (reference) 2C056 EA09 EA11 EA13 FC02 2H086 BA52 BA56 BA59 BA62 4J037 CB28 CC12 CC15 CC16 CC29 EE28 EE43 FF15 FF22 FF25 4J039 AD01 AD02 EA35 EA38 EA44 GA24

Claims (7)

[Claims] 1. A colored fine particle dispersion comprising colored fine particles containing an oil-soluble dye and a terminal-dissociable vinyl polymer. 2. The content of a dissociable group in a terminal dissociable vinyl polymer is 0.1 mmol / g or more and 2.0 mmo or less.
The colored fine particle dispersion according to claim 1, wherein the dispersion is 1 / g or less. 3. The colored fine particle dispersion according to claim 1, wherein the dissociable group of the terminal dissociable vinyl polymer is a carboxylic acid group or a sulfonic acid group. 4. The colored fine particle dispersion according to claim 1, wherein the oil-soluble dye is represented by the following general formula (I). General formula (I) (In the formula, Q represents an atomic group necessary for the compound represented by the general formula (I) to have an absorption in a visible region and / or a near-infrared region, A represents —NR ⁴ R ⁵ or a hydroxy group, R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, B ¹ is = C
(R ⁶ ) — or ＮN—, and B ² represents —C (R ⁷ ) =
Or represents -N =, represent R ^2, R ^3, R ⁶ and R ⁷ each independently represent a hydrogen atom or a substituent. R ² and R ³ ,
R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ^6, and R ⁶ and R ⁷ may combine with each other to form a ring. ) 5. The colored fine particles are produced by adding water to an organic solvent phase containing a terminally dissociable vinyl polymer and an oil-soluble dye or emulsifying the same by adding the organic solvent phase to water. The colored fine particle dispersion according to any one of claims 1 to 4, characterized in that: 6. An ink jet recording ink comprising the colored fine particle dispersion according to claim 1. Description: 7. An ink jet recording method, wherein recording is performed using the ink for ink jet recording according to claim 6.