JP2003176308A - Dye-containing resin fine particle and dispersion thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin fine particle containing oil-soluble dye and a dispersion thereof. <P>SOLUTION: This resin fine particle is obtained by subjecting an ethylenic monomer to emulsion polymerization in water or a liquid consisting essentially of water in the presence of a quinophthalone dye having a specific structure, a surfactant and a water-soluble polymerization initiator and contains ≥0.1 wt.% of the quinophthalone dye in the resin fine particle. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to resin fine particles and a dispersion thereof. More specifically, it relates to resin fine particles containing a specific quinophthalone dye and a dispersion thereof.

[0002]

2. Description of the Related Art As a method for preparing resin fine particles containing dyes and pigments, a method of obtaining colored resin fine particles by suspension polymerization / emulsion polymerization, a method of dyeing colorless resin fine particles with a dye, and the like have been proposed. There is. In recent years, the use of the microemulsion polymerization method or the miniemulsion polymerization method has been newly proposed. These resin particles have been
Widely used as paints, adhesives, surface treatment agents, inks, toners and other applications.

First, the colored resin fine particles obtained by the suspension polymerization method are fine particles having an average particle diameter of about 5 μm or more.
Not suitable as a colorant for ink because it is too large. Therefore, in recent years, a method for preparing colored fine particles by a microemulsion polymerization method or a miniemulsion polymerization method has been proposed, but in order to reduce the diameter of the obtained colored resin fine particles and narrow the particle size distribution, perturbation of ultrasonic waves, etc. It is necessary to obtain a monomer droplet preparation step that has an unstable factor in order to obtain complicated preparation reproducibility of the monomer oil droplet diameter such as adding a solvent.

In contrast to the above methodologies, the emulsion polymerization method forms resin fine particles in such a manner that the polymer is sequentially introduced into micelles.
Probabilistically, the polymer will be evenly distributed in every micelle, so the particle size distribution of the resin particles is narrower than that of the suspension polymerization method, miniemulsion polymerization method, or microemulsion polymerization method, and the average particle diameter is From about 5 nm to 500
It is easy to purposefully prepare up to about nm.

However, as an example of incorporating dyes or pigments into resin fine particles by emulsion polymerization, Japanese Patent Publication No. 52-2933
6, there are examples such as JP-A-10-251567, JP-A-2000-154341, etc., but there is no clear guideline of the dye species that can be particularly used until now, and the dye or pigment by emulsion polymerization is contained in the resin fine particles. There are few actual cases of research and development. That is,
In the emulsion polymerization method, the particle size distribution of the prepared resin fine particles is narrow and the particle size can be easily controlled, but in reality, the range of dyes that can be selected is limited. This is because it is not clear what structure the dye is suitable for when the dye is to be contained in the resin fine particles by emulsion polymerization.

[0006]

An object of the present invention is to obtain dye-containing resin fine particles by selecting an appropriate dye while making full use of the characteristics of the emulsion polymerization method.

[0007]

Therefore, the present inventors have
As a result of intensive studies to solve the above problems, if emulsion polymerization is carried out in the presence of a quinophthalone dye represented by the following general formula (I), a small particle size colored fine particle having a narrow particle size distribution and exhibiting a hue from red to blue is obtained. It has been found that can be practically produced. That is, the gist of the present invention is that, in water or a liquid containing water as a main component, an ethylenic monomer is present in the presence of a quinophthalone dye represented by the following general formula (I), a surfactant, and a water-soluble polymerization initiator. A resin fine particle obtained by emulsion polymerization of a monomer, wherein the quinophthalone dye is contained in the resin fine particle in an amount of 0.1% by weight or more.

[0008]

[Chemical 2]

(In the formula, X ^{1 to} X ¹⁰ are each independently a hydrogen atom,
Nitro group, hydroxy group, mercapto group, carboxyl group, cyano group, thiocyano group, halogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted Or unsubstituted heterocyclic group, substituted or unsubstituted amino group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted Heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkylsulfonyloxy group, substituted or unsubstituted arylsulfonyloxy group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted aryloxycarbonyloxy group, substituted Or not Alkoxycarbonyl group, substituted or unsubstituted cycloalkyloxycarbonyl group, substituted or unsubstituted alkenyloxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted heterocyclic oxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted Or unsubstituted sulfamoyl group, substituted or unsubstituted acyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted arylthio group A substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted alkoxysulfonyl group, a substituted or unsubstituted cycloalkyloxysulfonyl group, a substituted or unsubstituted alkenyloxysulfonyl group, a substituted or unsubstituted Lumpur oxysulfonyl group, or a substituted or unsubstituted heterocyclic oxysulfonyl group, X ⁷ and X ^8, X ⁸ and X ^9, X ⁹ and X ¹⁰
May together form a ring).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The resin fine particles of the present invention contain a quinophthalone dye represented by the following general formula (I), and the dispersion liquid is obtained by dispersing and emulsifying the resin fine particles in water or a liquid mainly composed of water. is there.

[0011]

[Chemical 3]

In the formula, X ^{1 to} X ¹⁰ are each independently a hydrogen atom, a nitro group, a hydroxy group, a mercapto group, a carboxyl group, a cyano group, a thiocyano group, a halogen atom, a substituted or unsubstituted alkyl, a substituted or unsubstituted cycloalkyl group. Alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted amino group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkyloxy group, substituted or Unsubstituted alkenyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkylsulfonyloxy group, substituted or unsubstituted arylsulfonyloxy group, substituted or Unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted Reeloxycarbonyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted cycloalkyloxycarbonyl group, substituted or unsubstituted alkenyloxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted heterocyclic oxycarbonyl group Group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, substituted or unsubstituted acyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted Cycloalkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkoxysulfonyl group, substituted or unsubstituted cycloalkyloxysulfonyl group, substituted or unsubstituted Luque alkenyloxy sulfonyl group, a substituted or unsubstituted aryloxy sulfonyl group, a substituted or represents one of unsubstituted heterocyclic oxysulfonyl group, X ⁷ and X ^8, X ⁸ and X ^9, X ⁹ and X ¹⁰
May together form a ring.

Examples of the halogen atom of X ^{1 to} X ¹⁰ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. X
^As the substituted or unsubstituted alkyl group of ^{1 to} X ^10, the unsubstituted alkyl group is a linear or branched alkyl group having 1 to 20 carbon atoms, specifically, methyl group, ethyl group, i-propyl group. Group, n-propyl group, i-butyl group,
Examples thereof include n-butyl group, pentyl group, hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, and n-dodecyl group, and the substituted alkyl group includes trifluoromethyl group, 2-chloroethyl group, Halogen atom-substituted alkyl group such as 2-bromoethyl group; Hydroxy group-substituted alkyl group such as 2-hydroxyethyl group and 3-hydroxyethyl group; Carboxyl group-substituted alkyl group such as carboxylmethyl group and 2-carboxyethyl group; 2-
Cyano group-substituted alkyl groups such as cyano group and ethyl group; 2
-Substituted or unsubstituted amino group-substituted alkyl group such as aminoethyl group, 2- (N-methylamino) ethyl group, 2- (N, N-dimethylamino) ethyl group; carbamoylmethyl group, N, N-dimethylcarbamoyl A substituted or unsubstituted carbamoyl group-substituted alkyl group such as an ethyl group; 2
A substituted or unsubstituted aryl group-substituted alkyl group such as a phenylethyl group or a 2- (p-methylphenyl) ethyl group; a substituted or unsubstituted alkoxy group-substituted alkyl group such as a 2-methoxyethyl group or a 2-methoxyethoxy group; Two
-Phenoxyethyl group, 2- (p-methylphenoxy)
Substituted or unsubstituted aryloxy group substituted alkyl group such as ethyl group; 2-acetoxyethyl group, substituted or unsubstituted acyloxy group substituted alkyl group such as 2- (p-chloro) benzoyloxyethyl group; cyclohexyloxymethyl group etc. Cycloalkyloxy group-substituted alkyl group; 2-methylthioethyl group, 3-ethylthiopropyl group, and other alkylthio group-substituted alkyl groups; Phenylthiomethyl group, 2- (p-methylphenylthio) ethyl group, etc., substituted or unsubstituted Arylthio group-substituted alkyl group;
Cycloalkylthio group-substituted alkyl group such as cyclohexylthiomethyl group; heterocyclic thio group-substituted alkyl group such as 2- (2-mercaptobenzothiazolyl) ethyl group;
A substituted or unsubstituted alkoxycarbonyl group-substituted alkyl group such as a methoxycarbonylmethyl group, a 2-ethoxycarbonylethyl group, a 2- (2-methoxyethoxy) carbonylethyl group; a 2-phenoxycarbonylethyl group,
A substituted or unsubstituted aryloxycarbonyl group-substituted alkyl group such as 2- (p-methoxyphenoxy) carbonylethyl group; a cycloalkyloxycarbonyl group-substituted alkyl group such as 2-cyclohexyloxycarbonylethyl group; a 2-carboxyethyl group, etc. Carboxyl group-substituted alkyl group; and mercapto group-substituted alkyl groups such as 2-mercaptoethyl group.

Examples of the substituted or unsubstituted cycloalkyl group of X ^{1 to} X ¹⁰ include those having 4 to 7 carbon atoms such as cyclopentyl group, cyclohexyl group and cycloheptyl group. The substituted or unsubstituted alkenyl group of X ^{1 to} X ¹⁰ includes a straight chain or branched chain having 2 to 10 carbon atoms, for example, vinyl group, allyl group, propenyl group, butenyl group, pentenyl group and the like. .

Examples of the substituted or unsubstituted aryl group of X ^{1 to} X ¹⁰ include a phenyl group and a naphthyl group, and those substituents include a linear or branched alkyl group having 1 to 10 carbon atoms and carbon number. 1 to 10 linear or branched alkoxy group, fluorine atom, chlorine atom, bromine atom,
Halogen atom such as iodine atom, trifluoromethyl group,
Examples thereof include substituted alkyl groups such as hydroxyethyl group and methoxyethyl group.

The substituted or unsubstituted heterocyclic group of X ^{1 to} X ¹⁰ is a pyridyl group, a quinolyl group, a furyl group, a pyranyl group, a pyrrolyl group, an imidazolyl group, an oxazolyl group,
Examples thereof include a pyrazolyl group, a thienyl group, a thiazolyl group, an isothiazolyl group, an isoxazolyl group, a pyrimidyl group, a triazinyl group, a benzothiazolyl group and a benzoxazolyl group, and a linear or branched group having 1 to 10 carbon atoms as a substituent thereof Chain alkyl group, carbon number 1-10
And linear or branched alkoxy groups, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, and substituted alkyl groups such as trifluoromethyl group, hydroxyethyl group and methoxyethyl group.

The substituent of the substituted amino group of X ^{1 to} X ¹⁰ is methyl group, ethyl group, propyl group, butyl group, octyl group, 2-ethylhexyl group, dodecyl group, 2-hydroxyethyl group, 2-methoxyethyl group. Group, 2- (2-methoxyethoxy) ethyl group, benzyl group, 2-phenethyl group, 2-chloroethyl group, tetrahydrofurfuryl group, or other substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; vinyl group, allyl group , An alkenyl group having 2 to 20 carbon atoms such as a propenyl group, a butenyl group, a pentenyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; a substituted or unsubstituted aryl group having 1 to 10 carbon atoms as a substituent. Chain or branched alkyl group, C1-C10 linear or branched alkoxy group, fluorine atom, chlorine Having a halogen atom such as a child, a bromine atom or an iodine atom, or a substituted alkyl group such as a trifluoromethyl group, a hydroxyethyl group or a methoxyethyl group, specifically, a phenyl group, a p-chlorophenyl group, or a m-methyl group. Phenyl group, p-methoxyphenyl group, p-cyanophenyl group, p-carboxyphenyl group, p-hydroxyphenyl group, p-mercaptophenyl group, p- (N, N-dimethylamino) phenyl group, p
-Nitrophenyl group, p-acetylphenyl group, substituted or unsubstituted aryl group such as 1-naphthyl group; pyridyl group, quinolyl group, furyl group, pyranyl group, pyrrolyl group, imidazolyl group, oxazolyl group, pyrazolyl group,
Substituted or unsubstituted heterocyclic group such as thienyl group, thiazolyl group, isothiazolyl group, isoxazolyl group, pyrimidyl group, triazinyl group, benzothiazolyl group, benzoxazolyl group; formyl group, acetyl group, propionyl group, butyryl group, octanoyl Group, benzoyl group, p-methylbenzoyl group, 1-naphthoyl group, thienoyl group and the like, substituted or unsubstituted acyl group having 1 to 20 carbon atoms; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, 2 A substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms such as a methoxyethylsulfonyl group; a phenylsulfonyl group,
a substituted or unsubstituted arylsulfonyl group such as p-methylphenylsulfonyl group, p-methoxyphenylsulfonyl group, p-chlorophenylsulfonyl group, 1-naphthylsulfonyl group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group A substituted or unsubstituted alkoxycarbonyl group such as benzyloxycarbonyl group; a substituted or unsubstituted aryloxycarbonyl group such as phenyloxycarbonyl group, p-methylphenyloxycarbonyl group, 1-naphthyloxycarbonyl group; cyclohexyloxycarbonyl group, Examples thereof include a cycloalkyloxycarbonyl group such as a cyclopentyloxycarbonyl group. The substituted amino group can have one or two of these substituents. Further, the nitrogen atom of the amino group and two substituents may be combined to form a 5-membered or 6-membered ring, and as the ring, a morpholine ring, a thiomorpholine ring, a piperidine ring, a piperazine ring, the following structure

[0018]

[Chemical 4]

And the like, and these rings may have a substituent. As the substituted or unsubstituted alkoxy group for X ^{1 to} X ^10, the unsubstituted alkoxy group is a linear or branched alkoxy group having 1 to 20 carbon atoms, specifically, a methoxy group, an ethoxy group, i- Propoxy group, n-propoxy group, i-butoxy group, n-butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, etc. As the substituted alkoxy group, the number of carbon atoms of the entire substituted alkoxy group is preferably 1 to 20, and 2-hydroxyethoxy group, 2-hydroxypropoxy group, 3-hydroxypropoxy group, 4-hydroxybutoxy group, etc. Hydroxy-substituted alkoxy group; benzyloxy group, p-chlorobenzyloxy group, 2-phenylethoxy group What phenyl-substituted alkoxy group; a 2-methoxyethoxy group, 2-
Ethoxyethoxy group, 2- (n) propoxyethoxy group, 2- (iso) propoxyethoxy group, 3-methoxypropoxy group, 4-methoxybutoxy group, 3-methoxybutoxy group, 2,3-dimethoxypropoxy group, 2,
Alkoxy-substituted alkoxy group such as 2-dimethoxyethoxy group; 2- (2-methoxyethoxy) ethoxy group, 2
-(2-ethoxyethoxy) ethoxy group, 2- (2-
(N) Propoxyethoxy) group, 2- (2- (n) butoxyethoxy) ethoxy group, 2- {2- (2-ethylhexyloxy) ethoxy} ethoxy group, and other alkoxyalkoxy-substituted alkoxy groups; 2-phenethyloxy Aralkyloxy-substituted alkoxy groups such as ethoxy group and 2-benzyloxyethoxy group; Acyloxy-substituted alkoxy groups such as 2-acetyloxyethoxy group, 2-propionyloxyethoxy group and 2-trifluoroacetyloxyethoxy group; 2-methoxycarbonyl Alkoxycarbonyl-substituted alkoxy groups such as ethoxy group and 2-ethoxycarbonylethoxy group; furfuryloxy group,
Heterocyclic-substituted alkoxy groups such as tetrahydrofurfuryloxy group; alkenyloxy-substituted alkoxy groups such as 2-allyloxyethoxy group; aryloxy-substituted alkoxy groups such as 2-phenoxyethoxy group and 2- (p-chlorophenoxy) ethoxy group And so on.

The substituted or unsubstituted cycloalkyloxy group for X ^{1 to} X ¹⁰ includes those having 4 to 7 carbon atoms, for example, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group and the like. The substituted or unsubstituted alkenyloxy group for X ^{1 to} X ¹⁰ has 2 to 12 carbon atoms.
Examples thereof include linear or branched 10 groups such as vinyloxy group, allyloxy group, propenyloxy group, butenyloxy group and pentenyloxy group.

Examples of the substituted or unsubstituted aryloxy group of X ^{1 to} X ¹⁰ include phenoxy group and naphthoxy group, and those substituents are nitro group; hydroxy group;
Mercapto group; carboxyl group; cyano group; thiocyano group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; linear or branched alkyl group having 1 to 10 carbon atoms; 1 to 10 carbon atom A linear or branched alkoxy group; and a substituted alkyl group such as trifluoromethyl group, hydroxyethyl group, methoxyethyl group and the like.

The substituted or unsubstituted heterocyclic oxy group for X ^{1 to} X ¹⁰ is a pyridyloxy group, a quinolyloxy group,
Furyloxy group, pyranyloxy group, pyrrolyloxy group, imidazolyloxy group, oxazolyloxy group, pyrazolyloxy group, thienyloxy group, thiazolyloxy group, isothiazolyloxy group, isoxazolyloxy group, pyrimidyloxy group, triazi Examples thereof include a nyloxy group, a benzothiazolyloxy group, a benzoxazolyloxy group, and the like, and the substituents thereof have 1 to 10 carbon atoms.
Linear or branched alkyl group having 1 to 1 carbon atoms
And straight chain or branched chain alkoxy groups of 0, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, and substituted alkyl groups such as trifluoromethyl group, hydroxyethyl group and methoxyethyl group. .

The substituted or unsubstituted acyloxy group of X ^{1 to} X ¹⁰ is acetyloxy group, propionyloxy group, butyryloxy group, octanoyloxy group, benzoyloxy group, p-methylbenzoyloxy group, 1-naphthoyloxy group. , Carbon number such as thienoyloxy group
-20 are mentioned. The substituted or unsubstituted alkylsulfonyloxy group for X ^{1 to} X ¹⁰ is a methylsulfonyloxy group, an ethylsulfonyloxy group, a propylsulfonyloxy group, a butylsulfonyl group oxy, a pentylsulfonyloxy group, a hexylsulfonyloxy group,
2-ethylhexylsulfonyloxy group, n-octylsulfonyloxy group, n-decylsulfonyloxy group,
Examples thereof include those having 1 to 20 carbon atoms such as n-dodecylsulfonyloxy group and 2-methoxyethoxysulfonyloxy group.

The substituted or unsubstituted arylsulfonyloxy group for X ^{1 to} X ¹⁰ is a phenylsulfonyloxy group, a p-methylphenylsulfonyloxy group, a p-methoxyphenylsulfonyloxy group, a p-chlorophenylsulfonyl group or a 1-naphthylsulfonyl group. Groups and the like. The substituted or unsubstituted alkoxycarbonyloxy group for X ^{1 to} X ¹⁰ is a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a propoxycarbonyloxy group, a butoxycarbonyloxy group, a pentyloxycarbonyloxy group, a hexyloxycarbonyloxy group, 2- Examples thereof include those having 1 to 20 carbon atoms such as an ethylhexyloxycarbonyloxy group, an n-octyloxycarbonyloxy group, an n-decyloxycarbonyloxy group, an n-dodecyloxycarbonyloxy group and a 2-methoxyethoxycarbonyloxy group.

The substituted or unsubstituted aryloxycarbonyloxy group for X ^{1 to} X ¹⁰ is a phenoxycarbonyloxy group, a p-methylphenoxycarbonyloxy group,
Examples thereof include p-methoxyphenoxycarbonyloxy group, p-chlorophenoxycarbonyloxy group and 1-naphthoxycarbonyloxy group. As the substituted or unsubstituted alkoxycarbonyl group of X ^{1 to} X ^10, the unsubstituted alkoxycarbonyl group has a linear or branched alkoxycarbonyl group having 1 to 20 carbon atoms, specifically methoxycarbonyl Group, ethoxycarbonyl group, i-propoxycarbonyl group, n-propoxycarbonyl group, i-butoxycarbonyl group, n-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-octyl Examples thereof include an oxycarbonyl group, an n-decyloxycarbonyl group, and an n-dodecyloxycarbonyl group. The substituted alkoxycarbonyl group preferably has 1 to 20 carbon atoms as the entire substituted alkoxy group, and 2-hydroxyethoxy. Carbonyl group,
-Hydroxypropoxycarbonyl group, 3-hydroxypropoxycarbonyl group, 4-hydroxybutoxycarbonyl group and other hydroxy-substituted alkoxycarbonyl groups; benzyloxycarbonyl group, p-chlorobenzyloxycarbonyl group, 2-phenylethoxycarbonyl group and other phenyl-substituted groups Alkoxycarbonyl group; 2-methoxyethoxycarbonyl group, 2-ethoxyethoxycarbonyl group, 2- (n) propoxyethoxycarbonyl group, 2- (iso) propoxyethoxycarbonyl group,
3-methoxypropoxycarbonyl group, 4-methoxybutoxycarbonyl group, 3-methoxybutoxycarbonyl group, 2,3-dimethoxypropoxycarbonyl group, 2,
Alkoxy-substituted alkoxycarbonyl group such as 2-dimethoxyethoxycarbonyl group; 2- (2-methoxyethoxy) ethoxy group carbonyl group, 2- (2-ethoxyethoxy) ethoxycarbonyl group, 2- (2- (n) propoxyethoxy) Carbonyl group, 2- (2- (n) butoxyethoxy) ethoxycarbonyl group, 2- {2- (2-
An alkoxyalkoxy-substituted alkoxycarbonyl group such as an ethylhexyloxy) ethoxy} ethoxycarbonyl group; a 2-phenethyloxyethoxycarbonyl group,
Aralkyloxy-substituted alkoxycarbonyl group such as 2-benzyloxyethoxycarbonyl group; Acyloxy-substituted alkoxycarbonyl group such as 2-acetyloxyethoxycarbonyl group, 2-propionyloxyethoxycarbonyl group, 2-trifluoroacetyloxyethoxycarbonyl group; 2 -Alkoxycarbonyl-substituted alkoxycarbonyl groups such as methoxycarbonylethoxycarbonyl group and 2-ethoxycarbonylethoxycarbonyl group; Heterocyclic-substituted alkoxycarbonyl groups such as furfuryloxycarbonyl group and tetrahydrofurfuryloxycarbonyl group; 2-allyloxyethoxycarbonyl Alkenyloxy-substituted alkoxycarbonyl group such as group; 2-phenoxyethoxycarbonyl group, 2- (p
And aryloxy-substituted alkoxycarbonyl groups such as -chlorophenoxy) ethoxycarbonyl group.

The substituted or unsubstituted cycloalkyloxycarbonyl group of X ^{1 to} X ¹⁰ has 4 to 7 carbon atoms,
Examples thereof include a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group and a cycloheptyloxycarbonyl group. The substituted or unsubstituted alkenyloxycarbonyl group of X ^{1 to} X ¹⁰ has a carbon number of 2 to
There may be mentioned linear or branched 10 groups such as vinyloxycarbonyl group, allyloxycarbonyl group, propenyloxycarbonyl group, butenyloxycarbonyl group and pentenyloxycarbonyl group.

Examples of the substituted or unsubstituted aryloxycarbonyl group of X ^{1 to} X ¹⁰ include phenoxycarbonyl group and naphthoxycarbonyl group, and those substituents are nitro group; hydroxy group; mercapto group; carboxyl group; cyano. Group; thiocyano group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; carbon number 1
A linear or branched alkyl group having 10 to 10; a linear or branched alkoxy group having 1 to 10 carbon atoms; a substituted alkyl group such as trifluoromethyl group, hydroxyethyl group, methoxyethyl group, etc. Can be mentioned.

The substituted or unsubstituted heterocyclic oxycarbonyl group of X ^{1 to} X ¹⁰ is a pyridyloxycarbonyl group, a quinolyloxycarbonyl group, a furyloxycarbonyl group, a pyranyloxycarbonyl group, a pyrrolyloxycarbonyl group, an imidazolyloxy group. Carbonyl group, oxazolyloxycarbonyl group, pyrazolyloxycarbonyl group, thienyloxycarbonyl group, thiazolyloxycarbonyl group, isothiazolyloxycarbonyl group, isoxazolyloxycarbonyl group, pyrimidyloxycarbonyl group, triazide Examples thereof include a nyloxycarbonyl group, a benzothiazolyloxycarbonyl group, and a benzoxazolyloxycarbonyl group. As a substituent thereof, a linear or branched alkyl group having 1 to 10 carbon atoms, or 1 carbon atom Linear or branched alkoxy groups of 10, a fluorine atom, a chlorine atom, a bromine atom,
Halogen atom such as iodine atom, trifluoromethyl group,
Examples thereof include substituted alkyl groups such as hydroxyethyl group and methoxyethyl group.

Examples of the substituent of the substituted carbamoyl group of X ^{1 to} X ¹⁰ include a methyl group, an ethyl group, a propyl group, a butyl group,
Octyl group, 2-ethylhexyl group, dodecyl group, 2-
Hydroxyethyl group, 2-methoxyethyl group, 2- (2
-Methoxyethoxy) ethyl group, benzyl group, 2-phenethyl group, 2-chloroethyl group, tetrahydrofurfuryl group, or other substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; vinyl group, allyl group, propenyl group, butenyl group ,
An alkenyl group having 2 to 20 carbon atoms such as a pentenyl group;
A cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a substituted or unsubstituted aryl group having a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, a linear or branched chain having 1 to 10 carbon atoms It has a chain alkoxy group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, or a substituted alkyl group such as a trifluoromethyl group, a hydroxyethyl group or a methoxyethyl group, and is specifically phenyl. Group, p-chlorophenyl group, m-methylphenyl group, p-methoxyphenyl group, p-cyanophenyl group, p-carboxyphenyl group, p-hydroxyphenyl group, p-mercaptophenyl group, p- (N, N- Dimethylamino) phenyl group, p
-Nitrophenyl group, p-acetylphenyl group, substituted or unsubstituted aryl group such as 1-naphthyl group; pyridyl group, quinolyl group, furyl group, pyranyl group, pyrrolyl group, imidazolyl group, oxazolyl group, pyrazolyl group,
Substituted or unsubstituted heterocyclic group such as thienyl group, thiazolyl group, isothiazolyl group, isoxazolyl group, pyrimidyl group, triazinyl group, benzothiazolyl group, benzoxazolyl group; formyl group, acetyl group, propionyl group, butyryl group, octanoyl Group, benzoyl group, p-methylbenzoyl group, 1-naphthoyl group, thienoyl group and the like, substituted or unsubstituted acyl group having 1 to 20 carbon atoms; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, 2 A substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms such as a methoxyethylsulfonyl group; a phenylsulfonyl group,
a substituted or unsubstituted arylsulfonyl group such as p-methylphenylsulfonyl group, p-methoxyphenylsulfonyl group, p-chlorophenylsulfonyl group, 1-naphthylsulfonyl group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group A substituted or unsubstituted alkoxycarbonyl group such as benzyloxycarbonyl group; a substituted or unsubstituted aryloxycarbonyl group such as phenyloxycarbonyl group, p-methylphenyloxycarbonyl group, 1-naphthyloxycarbonyl group; cyclohexyloxycarbonyl group, Examples thereof include a cycloalkyloxycarbonyl group such as a cyclopentyloxycarbonyl group. The substituted carbamoyl group can have one or two of these substituents. Further, the nitrogen atom of the carbamoyl group and two substituents may be combined to form a 5-membered or 6-membered ring, and as the ring, a morpholine ring, a thiomorpholine ring, a piperidine ring, a piperazine ring, the following structure

[0030]

[Chemical 5]

And the like, and these rings may have a substituent. Examples of the substituent of the substituted sulfamoyl group represented by X ^{1 to} X ¹⁰ include methyl group, ethyl group, propyl group, butyl group, octyl group, 2-ethylhexyl group, dodecyl group, 2-hydroxyethyl group, 2-methoxyethyl group, and 2 -(2-methoxyethoxy) ethyl group, benzyl group, 2-phenethyl group, 2-chloroethyl group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms such as tetrahydrofurfuryl group; vinyl group, allyl group, propenyl group , A alkenyl group having 2 to 20 carbon atoms such as a butenyl group and a pentenyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; a substituted or unsubstituted aryl group, which is a linear group having 1 to 10 carbon atoms as a substituent or Branched alkyl group, linear or branched alkoxy group having 1 to 10 carbon atoms, fluorine atom, chlorine atom Those having a halogen atom such as a bromine atom or an iodine atom, or a substituted alkyl group such as a trifluoromethyl group, a hydroxyethyl group or a methoxyethyl group, and specifically, a phenyl group, a p-chlorophenyl group, an m-methylphenyl group , P
-Methoxyphenyl group, p-cyanophenyl group, p-carboxyphenyl group, p-hydroxyphenyl group, p-
A substituted or unsubstituted aryl group such as mercaptophenyl group, p- (N, N-dimethylamino) phenyl group, p-nitrophenyl group, p-acetylphenyl group, 1-naphthyl group; pyridyl group, quinolyl group, furyl group , Pyranyl group, pyrrolyl group, imidazolyl group, oxazolyl group, pyrazolyl group, thienyl group, thiazolyl group, isothiazolyl group, isoxazolyl group, pyrimidyl group, triazinyl group, benzothiazolyl group, benzoxazolyl group, etc. Ring group; formyl group,
A substituted or unsubstituted acyl group having 1 to 20 carbon atoms such as acetyl group, propionyl group, butyryl group, octanoyl group, benzoyl group, p-methylbenzoyl group, 1-naphthoyl group, thienoyl group; methylsulfonyl group, ethylsulfonyl group 1 to 1 carbon atoms such as propylsulfonyl group, butylsulfonyl group and 2-methoxyethylsulfonyl group
20 substituted or unsubstituted alkylsulfonyl groups; phenylsulfonyl groups, p-methylphenylsulfonyl groups, p
-Substituted or unsubstituted arylsulfonyl group such as methoxyphenylsulfonyl group, p-chlorophenylsulfonyl group, 1-naphthylsulfonyl group; substitution of methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, benzyloxycarbonyl group, etc. Or an unsubstituted alkoxycarbonyl group;
A substituted or unsubstituted aryloxycarbonyl group such as a phenyloxycarbonyl group, a p-methylphenyloxycarbonyl group, a 1-naphthyloxycarbonyl group; a cycloalkyloxycarbonyl group such as a cyclohexyloxycarbonyl group and a cyclopentyloxycarbonyl group. . The substituted sulfamoyl group can have one or two of these substituents. Further, the nitrogen atom of the sulfamoyl group and two substituents may be combined to form a 5-membered or 6-membered ring, and as the ring, a morpholine ring, a thiomorpholine ring, a piperidine ring, a piperazine ring, the following structure

[0032]

[Chemical 6]

And the like, and these rings may have a substituent. The substituted or unsubstituted acyl group of X ^{1 to} X ¹⁰ is formyl group, acetyl group, propionyl group, butyryl group, octanoyl group, benzoyl group, p
Examples thereof include a substituted or unsubstituted acyl group having 1 to 20 carbon atoms such as a methylbenzoyl group, a 1-naphthoyl group and a thienoyl group.

The substituted or unsubstituted alkylsulfonyl group is a linear or branched alkylkisulfonyl group having 1 to 20 carbon atoms, specifically a methylsulfonyl group,
Ethylsulfonyl group, i-propylsulfonyl group, n-
Propylsulfonyl group, i-butylsulfonyl group, n-
Butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, 2-ethylhexylsulfonyl group, n-
Octylsulfonyl group, n-decylsulfonyl group, n-
Examples thereof include dodecylsulfonyl group, which may have a substituent such as a halogen atom, a hydroxy group and an alkoxy group.

Examples of the substituted or unsubstituted arylsulfonyl group of X ^{1 to} X ¹⁰ include phenylsulfonyl group and naphthylsulfonyl group, and those substituents have 1 carbon atoms.
-10 straight-chain or branched-chain alkyl group, C1-C10 straight-chain or branched-chain alkoxy group, halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, trifluoromethyl Group, hydroxyethyl group,
Examples thereof include a substituted alkyl group such as a methoxyethyl group.

The substituted or unsubstituted alkylthio group of X ^{1 to} X ¹⁰ is a linear or branched alkylchithio group having 1 to 20 carbon atoms, specifically, methylthio group, ethylthio group, i-propylthio group, n -Propylthio group, i
-Butylthio group, n-butylthio group, pentylthio group,
A hexylthio group, a 2-ethylhexylthio group, an n-octylthio group, an n-decylthio group, an n-dodecylthio group and the like can be mentioned, and these are a halogen atom, a hydroxy group,
It may have a substituent such as an alkoxy group.

Examples of the substituted or unsubstituted cycloalkylthio group of X ^{1 to} X ¹⁰ include those having 4 to 7 carbon atoms, such as cyclopentylthio group, cyclohexylthio group and cycloheptylthio group. Examples of the substituted or unsubstituted arylthio group for X ^{1 to} X ¹⁰ include a phenylthio group and a naphthylthio group, and those substituents have 1 to 1 carbon atoms.
0 straight-chain or branched-chain alkyl group, 1 to 1 carbon atoms
And 10 linear or branched alkoxy groups, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, and substituted alkyl groups such as trifluoromethyl group, hydroxyethyl group and methoxyethyl group. .

The substituted or unsubstituted heterocyclic thio group for X ^{1 to} X ¹⁰ is a pyridylthio group, a quinolylthio group, a furylthio group, a pyranylthio group, a pyrrolylthio group, an imidazolylthio group, an oxazolylthio group, a pyrazolylthio group,
Examples thereof include thienylthio group, thiazolylthio group, isothiazolylthio group, isoxazolylthio group, pyrimidylthio group, triazinylthio group, benzothiazolyl group thio, benzoxazolylthio group, and the like. A chain or branched alkyl group, a linear or branched alkoxy group having 1 to 10 carbon atoms, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a trifluoromethyl group, hydroxyethyl Group, a substituted alkyl group such as a methoxyethyl group, and the like.

As the substituted or unsubstituted alkoxysulfonyl group of X ^{1 to} X ^10, the unsubstituted alkoxysulfonyl group has a linear or branched alkoxysulfonyl group having 1 to 20 carbon atoms, specifically, Is a methoxysulfonyl group, ethoxysulfonyl group, i-propoxysulfonyl group, n-propoxysulfonyl group, i-butoxysulfonyl group, n-butoxysulfonyl group, pentyloxysulfonyl group, hexyloxysulfonyl group, 2-ethylhexyloxysulfonyl group, n-octyloxysulfonyl group, n-decyloxysulfonyl group, n-dodecyloxysulfonyl group and the like,
The substituted alkoxysulfonyl group preferably has 1 to 20 carbon atoms as the entire substituted alkoxy group, and includes 2-hydroxyethoxysulfonyl group, 2-hydroxypropoxysulfonyl group, 3-hydroxypropoxysulfonyl group, 4-hydroxybutoxysulfonyl group. A hydroxy-substituted alkoxysulfonyl group such as a group; a benzyloxysulfonyl group, a p-chlorobenzyloxysulfonyl group,
Phenyl-substituted alkoxysulfonyl group such as 2-phenylethoxysulfonyl group; 2-methoxyethoxysulfonyl group, 2-ethoxyethoxysulfonyl group, 2-
(N) propoxyethoxysulfonyl group, 2- (is
o) Alkoxy-substituted alkoxy such as propoxyethoxysulfonyl group, 3-methoxypropoxysulfonyl group, 4-methoxybutoxysulfonyl group, 3-methoxybutoxysulfonyl group, 2,3-dimethoxypropoxysulfonyl group, 2,2-dimethoxyethoxysulfonyl group. Sulfonyl group; 2- (2-methoxyethoxy) ethoxysulfonyl group, 2- (2-ethoxyethoxy) ethoxysulfonyl group, 2- (2- (n) propoxyethoxy)
Alkoxyalkoxy-substituted alkoxycarbonyl groups such as sulfonyl group, 2- (2- (n) butoxyethoxy) ethoxysulfonyl group, 2- {2- (2-ethylhexyloxy) ethoxy} ethoxysulfonyl group; 2-phenethyloxyethoxysulfonyl Group, aralkyloxy-substituted alkoxysulfonyl group such as 2-benzyloxyethoxysulfonyl group; acyloxy-substituted alkoxysulfonyl group such as 2-acetyloxyethoxysulfonyl group, 2-propionyloxyethoxysulfonyl group, 2-trifluoroacetyloxyethoxysulfonyl group 2-methoxycarbonylethoxysulfonyl group, 2
An alkoxycarbonyl-substituted alkoxysulfonyl group such as an ethoxycarbonylethoxysulfonyl group; a heterocyclic-substituted alkoxysulfonyl group such as a furfuryloxysulfonyl group and a tetrahydrofurfuryloxysulfonyl group; an alkenyloxy-substituted alkoxysulfonyl group such as a 2-allyloxyethoxysulfonyl group Group; an aryloxy-substituted alkoxysulfonyl group such as a 2-phenoxyethoxysulfonyl group and a 2- (p-chlorophenoxy) ethoxysulfonyl group.

The substituted or unsubstituted cycloalkyloxysulfonyl group of X ^{1 to} X ¹⁰ has 4 to 7 carbon atoms,
For example, a cyclopentyloxy sulfonyl group, a cyclohexyl oxy sulfonyl group, a cycloheptyl oxy sulfonyl group etc. are mentioned. The substituted or unsubstituted alkenyloxysulfonyl group of X ^{1 to} X ¹⁰ has 2 to 12 carbon atoms.
Examples thereof include linear or branched 10 groups such as vinyloxysulfonyl group, allyloxysulfonyl group, propenyloxysulfonyl group, butenyloxysulfonyl group and pentenyloxysulfonyl group.

Examples of the substituted or unsubstituted aryloxysulfonyl group of X ^{1 to} X ¹⁰ include a phenoxysulfonyl group and a naphthoxysulfonyl group, and those substituents include a nitro group; a hydroxy group; a mercapto group; a carboxyl group; a cyano group. Group; thiocyano group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; carbon number 1
A linear or branched alkyl group having 10 to 10; a linear or branched alkoxy group having 1 to 10 carbon atoms; a substituted alkyl group such as trifluoromethyl group, hydroxyethyl group, methoxyethyl group, etc. Can be mentioned.

The substituted or unsubstituted heterocyclic oxysulfonyl group of X ^{1 to} X ¹⁰ is a pyridyloxysulfonyl group, a quinolyloxysulfonyl group, a furyloxysulfonyl group, a pyranyloxysulfonyl group, a pyrrolyloxysulfonyl group, an imidazolyloxy group. Sulfonyl group, oxazolyloxysulfonyl group, pyrazolyloxysulfonyl group, thienyloxysulfonyl group, thiazolyloxysulfonyl group, isothiazolyloxysulfonyl group, isoxazolyloxysulfonyl group, pyrimidyloxysulfonyl group, triazine Examples thereof include a nyloxysulfonyl group, a benzothiazolyloxysulfonyl group, a benzoxazolyloxysulfonyl group, and the like, and their substituents are a linear or branched alkyl group having 1 to 10 carbon atoms and a carbon number of 1 Linear or branched alkoxy groups of 10, a fluorine atom, a chlorine atom, a bromine atom,
Halogen atom such as iodine atom, trifluoromethyl group,
Examples thereof include substituted alkyl groups such as hydroxyethyl group and methoxyethyl group.

Examples of X ⁷ and X ⁸ , X ⁸ and X ⁹ , and X ⁹ and X ¹⁰ which together form a ring include the following structures (II) and (II
I), (IV) and the like.

[0044]

[Chemical 7]

(In the formula, X ^{1 to} X ¹⁰ have the same meanings as in the formula (I), and the ring A may have any nonionic substituent.)

[0046]

[Chemical 8]

(In the formula, X ^{1 to} X ¹⁰ have the same meanings as in the formula (I), and the ring B may have any nonionic substituent)

[0048]

[Chemical 9]

(In the formula, X ^{1 to} X ¹⁰ have the same meanings as in formula (I), and X ¹¹ and X ¹² represent an oxygen atom, a sulfur atom or NH.
X ¹³ represents a substituted or unsubstituted alkyl group, an alkenyl group, a cycloalkyl group or an aryl group.) Particularly preferable examples include a quinophthalone compound represented by the following structural formula (V). .

[0050]

[Chemical 10]

(In the formula, Y ² is a hydrogen atom, a halogen atom,
A substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, Y ³ , Y ⁴ , Y ⁵ and Y ⁶ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, Y ⁷ and Y ¹⁰ is a hydrogen atom or a halogen atom, Y ⁸ and Y ⁹ are a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a mercapto group, a carboxyl group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group , Substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkylsulfonyloxy group, substituted or unsubstituted arylsulfonyloxy group, substituted or unsubstituted Alkoxycarbonyl group, substituted or unsubstituted cycloalkyloxycarbonyl group, substituted or Unsubstituted alkenyloxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted arylthio Group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkoxysulfonyl group, substituted or unsubstituted cycloalkyloxysulfonyl group, substituted or unsubstituted alkenyloxysulfonyl group, substituted or unsubstituted aryloxysulfonyl group And Y ⁸ and Y ⁹ may together form a ring.) Preferred quinophthalone dye compound examples are shown below.

[0052]

[Chemical 11]

[0053]

[Chemical 12]

[0054]

[Chemical 13]

[0055]

[Chemical 14]

[0056]

[Chemical 15]

[0057]

[Chemical 16]

[0058]

[Chemical 17]

[0059]

[Chemical 18]

The method for producing the resin fine particle dispersion of the present invention is not particularly limited, and it can be produced by an emulsion polymerization method, a suspension polymerization method, or a polymerization method such as a miniemulsion or a microemulsion, but the particle size distribution can be controlled. It is preferable to use the emulsion polymerization method because it is easy to process. In order to produce the resin fine particle dispersion of the present invention by an emulsion polymerization method, typically, anthraquinone dye having a solubility in water of 0.0001 to 10 g / l and a solubility in toluene of 10 to infinite g / l is used. The contained monomer (may be a mixture) is dispersed in water or a liquid mainly composed of water in the presence of a surfactant, and a water-soluble polymerization initiator is added to carry out polymerization.

As the latex resin contained in the resin particle dispersion of the present invention, a resin obtained by emulsion polymerization can be used, and a monomer (ethylenic monomer) constituting the resin is preferably styrene, Parachlorostyrene, α
-Homopolymers or copolymers of styrenes such as methylstyrene (styrene resins); vinyl acetate; methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, acrylic acid Two
-Homopolymers or copolymers (vinyl-based resins) of esters having a vinyl group such as ethylhexyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; acrylonitrile, Homopolymers or copolymers of vinyl nitriles such as methacrylonitrile (vinyl resin); Homopolymers or copolymers of vinyl ethers such as vinyl methyl ether, vinyl isobutyl ether (vinyl resin); Vinyl methyl ketone , Vinyl ethyl ketone, vinyl isopropenyl ketone and other vinyl ketone homopolymers or copolymers (vinyl resins); ethylene,
Homopolymers or copolymers of olefins such as propylene, butadiene and isoprene (olefin resins); non-vinyl condensation resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins and polyether resins, and Examples thereof include graft polymers of these non-vinyl condensation resins and vinyl monomers.
These resins may be used alone or in combination of two or more.

Among these resins, styrene resins,
Vinyl-based resin, polyester resin, olefin-based resin is preferable, a copolymer of styrene and butyl acrylate,
Butyl acrylate, bisphenol A / fumaric acid copolymer, and copolymer of styrene and olefin are particularly preferable. In producing the resin fine particles of the present invention, the monomer constituting the resin and the quinophthalone dye are emulsified in the presence of an emulsifier, a polymerization initiator is added, and polymerization is carried out according to a standard method.

The emulsifier is selected from known cationic surfactants, anionic surfactants and nonionic surfactants, and two or more kinds thereof may be used in combination. Specific examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like.

Specific examples of the anionic surfactant include sodium stearate, sodium dodecanoate,
And fatty acid soaps such as sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate and the like. Furthermore, specific examples of nonionic surfactants include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, nonylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, and monodecanoyl. Examples include sucrose.

The polymerization initiator is used in the case of carrying out emulsion polymerization.
A water-soluble or oil-soluble one is used. For example, potassium persulfate, sodium persulfate, ammonium persulfate alone, or an initiator system in which a redox system of iron trivalent ion-containing inorganic salt or organic salt with them is constructed, and other redox systems include hydrogen peroxide and ascorbic acid. A redox type polymerization initiator in which the above are combined is preferable.

The content of the quinophthalone dye is 0.1% by weight or more in the resin fine particles, and although it depends on the indispensable amount of the quinophthalone dye used, it is usually 1 to 100 parts by weight, preferably 100 parts by weight of the binder resin. It is used so as to be 3 to 50 parts by weight. These quinophthalone dyes are used by being dissolved in oil droplets of a monomer dispersed in water in the presence of an emulsifier in the emulsion polymerization step, and used in resin particles produced by the emulsion polymerization.

In the emulsion polymerization process, considering that the quinophthalone dye moves into the micelle together with the polymer, it is better to dissolve it slightly in water. Therefore, the solubility of the colorant in water is 0.0001 to 10 g. / L is preferable, and 0.001 to 5 g / l is more preferable. Further, in the emulsion polymerization step, the colorant should be dissolved in the oil droplets of the monomer, so the solubility in toluene is preferably 5 to infinite g / l, more preferably 20 to 1000 g / l, and even more preferably 30 to 300 g / l. Particularly preferred.

The volume average particle diameter of the resin fine particles including the surface active agent layer around the resin is 200 nm or less, preferably 120 nm or less, more preferably 8 nm or less.
It is 0 nm or less, particularly 70 nm or less. When the volume average particle diameter is larger than the above range, self-organization is difficult to be exhibited. The lower limit of the volume average particle diameter of the resin fine particles is usually 5 nm in consideration of the presence of the surfactant layer, but if the volume average particle diameter is extremely small, it may be necessary to use the resin in the dispersion liquid. Since the proportion of resin is too low, 10
nm or more is preferable. The average particle diameter can be measured with an optical Doppler particle size distribution meter (“MICROTRAC particle size distribution meter” manufactured by Nikkiso Co., Ltd.), or resin particles are used as a transmission electron microscope (TEM) (for example, Hitachi H-9000NA).
It can be measured by taking an image of the photograph and analyzing the image.

The solid content concentration of the resin fine particle dispersion is usually 10 to 50%, and it can be appropriately diluted before use. The quinophthalone dye-containing resin fine particle dispersion liquid described above is prepared by dropping 0.5 ml of the resin fine particle dispersion liquid on a recycled paper having a thickness of about 60 μm (KOKUYO Co., Ltd. product number “Hi-501N”). It is preferable that the amount of permeated water after 5 minutes has passed is 1 mg or less.

Further, in order to facilitate the expression of self-organization, it is preferable that the particle size distribution is small and the particles have the same shape, so that the volume average particle size (DV) of the resin fine particles.
And the number average particle size (DN) are 1 ≦ DV / DN ≦
1.5 is preferable, 1 ≦ DV / DN ≦ 1.4
Is more preferable, and 1 ≦ DV / DN ≦ 1.3 is particularly preferable.

As a more detailed practical example, when the resin fine particles are oil-soluble dyes as quinophthalone type dyes, resin fine particle dispersions that can be used in water-based paint inks, printer inks that can achieve high resolution, etc. It becomes liquid. When the above resin dispersion liquid is used as a coating material, an aqueous binder resin can be added and used. Examples of the aqueous binder resin include water-soluble resins such as polyvinylpyrrolidone and polyvinyl alcohol, acrylic emulsions, vinyl acetate emulsions, styrene emulsions, epoxy resin emulsions, urethane resin emulsions, silicone resin emulsions,
Examples thereof include emulsion liquids of resins such as fluororesin emulsion, rubber latex and polyolefin resin emulsion. If necessary, a water-miscible solvent,
A surfactant, a viscosity adjusting agent, an antioxidant, a light stabilizer, an ultraviolet absorber, a mildew proofing agent, an anti-drying agent and the like can be added and used. As the solvent and the surfactant, the same substances as those shown in the ink can be mentioned.

When the above-mentioned resin dispersion liquid is used as an ink, it can be used as it is, but if necessary, a water-miscible solvent, a surfactant, a viscosity adjusting agent, an antioxidant, It is also possible to add and use a light stabilizer, an ultraviolet absorber, an antifungal agent, an anti-drying agent and the like. Examples of the solvent include ethanol, isopropanol, ethylene glycol, propylene glycol,
Butylene glycol, diethylene glycol, polyethylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethylene uricol monoallyl ether, 2-pyrrolidone,
N-methylpyrrolidone, 1,3-dimethylimidazolidinone, thiodiethanol, sulfolane, dimethyl sulfoxide and the like can be mentioned. As the surfactant, known cationic surfactants, anionic surfactants and nonionic surfactants can be used. Two or more selected may be used in combination.

Specific examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like. Specific examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate and the like.

Further, specific examples of the nonionic surfactant include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, nonylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, Examples include monodecanoyl sucrose and the like.

These inks are used for ink jet recording,
It can be used for writing instruments, printing, etc., but is particularly suitable for inkjet recording.

[0076]

EXAMPLES Specific examples of preparation of a quinophthalone dye-containing resin fine particle dispersion will be shown below as examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. In the following, "part" means "part by weight". [Example 1] (Preparation of quinophthalone dye-encapsulated resin fine particle dispersion liquid) A glass reactor equipped with a stirrer, a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device was charged with the following amount of 10% N-
Sodium dodecylbenzene sulfonate (S-DBS)
12 parts of an aqueous solution and 383 parts of demineralized water were charged, and the temperature was raised to 90 ° C. under a nitrogen stream.

Then, an oil-soluble dye (compound D-1) was dissolved in the following monomers and dispersed in an emulsifier aqueous solution. Then, a polymerization initiator was added to the emulsion liquid heated to 90 ° C., and emulsion polymerization was performed for 6.5 hours.

[0078]

[Table 1] (Monomers) Styrene 79 parts Butyl acrylate 21 parts Acrylic acid 3 parts Trichlorobromomethane (TCBM) 0.5 parts Mercaptoethanol (MPE) 0.01 parts (Oil-soluble dye) Compound of D-1 9 parts (emulsifier aqueous solution) sodium dodecylbenzenesulfonate 10% aqueous solution 8 parts demineralized water 18 parts (polymerization initiator) 8% hydrogen peroxide aqueous solution 10.6 parts 8% ascorbic acid aqueous solution 10.6 parts Cooling after completion of polymerization reaction A yellow polymer dispersion was obtained. The solid content concentration of the obtained polymer dispersion was 17.6%,
The yield was 88%.

As a result, the volume average particle diameter was 17 nm and D
V / DN = 1.3. This resin particle dispersion liquid.
Recycled paper with 6 layers of 5 ml (Kokuyo Co., Ltd., product number “Hi-5
01N ") and placed for 5 minutes with a pipette, but neither bleeding nor yellow coloration on the second sheet from the top, water in the resin particles did not penetrate the recycled paper. . [Example 2] (Example of ink production and evaluation) The dye-containing resin fine particle dispersion prepared in Example 1 above was mixed with
An aqueous solution of sodium dodecylbenzene sulfonate and water were mixed to obtain 10% by weight of dye-containing resin fine particles,
It was prepared so that sodium dodecylbenzenesulfonate was 4% by weight. Kiriyama No. 5C
An ink was obtained by pressure filtration with nitrogen gas using a (1 micron) filter paper.

This ink was put in a cartridge of an ink jet printer (Epson PM-670C), and a print test pattern was printed on plain paper. As a result, the printed matter is
It is excellent in color development and has excellent water resistance as much as pigment ink.
Moreover, a printed matter having excellent abrasion resistance was obtained. [Comparative Example 1] A glass reactor equipped with a stirrer, a heating / cooling device, a concentrator, and a raw material / auxiliary charging device was charged with the following amount of 10% sodium N-dodecylbenzenesulfonate (S-DBS) aqueous solution 12 parts and 383 parts of demineralized water were charged and heated to 90 ° C. under a nitrogen stream.

Then, an oil-soluble dye (compound (A) below) was dissolved in the following monomers and dispersed in an aqueous emulsifier solution. Then, a polymerization initiator was added to the emulsion liquid heated to 90 ° C., and emulsion polymerization was performed for 6.5 hours.

[0082]

[Table 2]     (Monomers)   Styrene 79 parts   Butyl acrylate 21 parts   Acrylic acid 3 parts   Trichlorobromomethane (TCBM) 0.5 parts   Mercaptoethanol (MPE) 0.01 parts     (Oil-soluble dye)   10 parts of the following compound (A)     (Aqueous emulsifier solution)   Sodium dodecylbenzene sulfonate 10% aqueous solution 8 parts   18 parts of demineralized water

[0083]

[Chemical 19]

(Polymerization initiator) 8% hydrogen peroxide aqueous solution 10.6 parts 8% ascorbic acid aqueous solution 10.6 parts During the polymerization, the monomer phase in which the compound A was dissolved and the aqueous solution phase of the solvent were separated. After the completion of the polymerization reaction, the mixture was cooled and the solid content concentration of the polymer dispersion was measured, but it was 2% or less, and colored fine particles containing the dye could not be prepared by emulsion polymerization.

[0085]

According to the present invention, it is possible to provide a dye-containing resin fine particle dispersion liquid which can be applied to an ink for water-based paints and an ink for printers which can achieve high resolution.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Akira Nemoto, the inventor             1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa             Within Mitsubishi Chemical Corporation (72) Inventor Yukichi Murata             1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa             Within Mitsubishi Chemical Corporation (72) Inventor Miori Ishida             1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa             Within Mitsubishi Chemical Corporation F-term (reference) 4J002 BB021 BB111 BB171 BC021                       BC111 BE041 BE051 BF021                       BG041 BG051 BG061 BG101                       BN171 CH022 EG027 EN137                       EU056 EV257 FD096 FD312                       FD317 GT00 HA07                 4J011 KA02 KA08 KA10 KA15 KB08                       PA43 PB25 PC06

Claims (5)

[Claims] 1. An ethylenic monomer in the presence of a quinophthalone dye represented by the following general formula (I), a surfactant, and a water-soluble polymerization initiator in water or a liquid containing water as a main component. Resin fine particles obtained by emulsion-polymerizing, wherein the quinophthalone dye is contained in the resin fine particles in an amount of 0.1% by weight or more. [Chemical 1] (In the formula, X ^{1 to} X ¹⁰ are each independently a hydrogen atom, a nitro group, a hydroxy group, a mercapto group, a carboxyl group, a cyano group, a thiocyano group, a halogen atom, a substituted or unsubstituted alkyl, a substituted or unsubstituted cycloalkyl group. A substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted Alkenyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkylsulfonyloxy group, substituted or unsubstituted arylsulfonyloxy group, substituted or unsubstituted An alkoxycarbonyloxy group, a substituted or unsubstituted aryl group Sicarbonyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted cycloalkyloxycarbonyl group, substituted or unsubstituted alkenyloxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted heterocyclic oxycarbonyl group A substituted or unsubstituted carbamoyl group,
Substituted or unsubstituted sulfamoyl group, substituted or unsubstituted acyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted arylthio Group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkoxysulfonyl group, substituted or unsubstituted cycloalkyloxysulfonyl group, substituted or unsubstituted alkenyloxysulfonyl group, substituted or unsubstituted aryloxysulfonyl group,
It represents either a substituted or unsubstituted heterocyclic oxysulfonyl group, and X ⁷ and X ⁸ , X ⁸ and X ⁹ , and X ⁹ and X ¹⁰ may together form a ring). 2. The volume average particle diameter (DV) is 5 nm or more 20.
0 nm or less, and the relationship between the volume average particle diameter (DV) and the number average particle diameter (DN) is 1 ≦ DV / DN ≦ 1.5.
2. The resin fine particles according to claim 1, wherein 3. A resin fine particle dispersion liquid comprising the resin fine particles according to claim 1 or 2 emulsified and dispersed in water or a liquid containing water as a main component. 4. An ink using the fine resin particle dispersion according to claim 1. 5. A coating material using the resin fine particle dispersion liquid according to claim 1.