JP2002285027A - Resin fine particle including dye and its dispersion liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin fine particle including an oil-soluble dye and its dispersion liquid. SOLUTION: The resin fine particle is obtained by emulsion polymerization of an ethylene monomer in the presence of an anthraquinone dye with a specific structure, a surfactant and a water-soluble polymerization initiator in water or in a liquid consisting of water as a main component and the resin fine particle has a feature to include 0.1% or more of the anthraquinone dye.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin fine particle and the dispersion liquid. BACKGROUND OF THE INVENTION More specifically, the present invention relates to resin fine particles containing a specific anthraquinone dye and a dispersion thereof.

[0002]

2. Description of the Related Art As a method for preparing fine resin particles containing a dye or a pigment, a method of obtaining colored resin fine particles by performing suspension polymerization or emulsion polymerization or a method of dyeing colorless resin fine particles with a dye have been proposed. I have. In recent years, use of a microemulsion polymerization method or a miniemulsion polymerization method has been newly proposed. These resin particles have been
It is widely used for paints, adhesives, surface treatment agents, inks, toners and other uses.

[0003] First, the colored resin fine particles obtained by suspension polymerization have an average particle size of more than about 5μm particles obtained, paints and
It is too large to be suitable as a colorant for ink. Therefore, in recent years, a method of preparing colored fine particles by a micro-emulsion polymerization method or a mini-emulsion 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 or the like is performed. it is necessary to obtain a monomer droplet preparation step facing the instability to get complicated and preparation reproducibility of monomer oil droplet diameter such added.

[0004] In contrast to the above-mentioned methodology, in the emulsion polymerization method, resin fine particles are formed in such a manner that a polymer enters a micelle sequentially.
Probabilistically, the polymer will enter the micelles evenly, so that the particle distribution of the resin fine particles is narrower than that obtained by the suspension polymerization method, the mini-emulsion polymerization method, or the micro-emulsion polymerization method, and the average particle diameter is smaller. From 5nm to 500
It is easy to prepare for the purpose up to about nm.

However, as an example of incorporating dyes and pigments into resin fine particles by emulsion polymerization, Japanese Patent Publication No.
6, JP-A 10-251567, there is an embodiment of such JP 2000-154341A Although there is no clear guidance especially available dye species to date, containing a dye or pigment by emulsion polymerization in the resin particles research and development example in which there is little actual situation. 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 the actual dye range is limited. This is due to the fact that it is not clear what dye structure is suitable when the dye is to be contained in the resin fine particles by emulsion polymerization.

[0006]

An object of the present invention is to provide a while utilizing more than enough features emulsion polymerization method, an object is to obtain a dye-containing resin particles by selecting appropriate dyes.

[0007]

Means for Solving the Problems Accordingly, the present inventors have:
Result of intensive studies to solve the above problems, by performing an emulsion polymerization in the presence of anthraquinone dye represented by the following general formula (I), the small particles sized colored particles narrow particle size distribution exhibiting a blue hue from red Can be produced practically. That is, the gist of the present invention is to provide an ethylenic monomer in water or a liquid mainly containing water in the presence of an anthraquinone dye represented by the following general formula (I), a surfactant, and a water-soluble polymerization initiator. Resin fine particles obtained by emulsion polymerization of a monomer, wherein an anthraquinone-based dye is contained in the resin fine particles in an amount of 0.1% or more.

[0008]

Embedded image (Wherein X ^{1 to} X ⁸ each independently represent a hydrogen atom, a nitro group, a hydroxy group, a mercapto group, a carboxyl group, a 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 an unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted substituted alkylsulfonyloxy group, a substituted or unsubstituted arylsulfonyloxy group, a substituted or unsubstituted alkoxycarbonyloxy group, a substituted or unsubstituted aryloxycarbonyloxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted cycloalkyloxy Ca Bonyl 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, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group ,, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted arylthio group, a 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, substituted or unsubstituted heterocyclic oxysulfonyl group Represents Le group, X
² and X ³ may combine with each other to form a ring).

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Fine resin particles of the present invention contains the anthraquinone dye represented by the following formula (I), the dispersion is dispersed in the liquid to the resin fine particles mainly composed of water or water made of emulsified is there.

[0010]

Embedded image (Wherein, X ¹ to X ⁸ are each independently a hydrogen atom, a nitro group, hydroxy group, a mercapto group, a carboxyl group, a 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 an unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted Substituted alkylsulfonyloxy group, substituted or unsubstituted arylsulfonyloxy group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted aryloxycarbonyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted cycloalkyloxy group Bonyl 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, 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, substituted or unsubstituted heterocyclic oxysulfonyl group Represents Le group, X
² and X ³ may be bonded to form a ring together).

The halogen atom of X ^{1 to} X ⁸ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. X ¹
As a substituted or unsubstituted alkyl group to X ^8, unsubstituted, straight or branched Arukiruki group having 1 to 20 carbon atoms as the alkyl group, specifically a methyl group, an ethyl group,
i- propyl group, n- propyl group, i- butyl, n-
Butyl group, pentyl group, hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group, and the like. Examples of the substituted alkyl group include a trifluoromethyl group, a 2-chloroethyl group, and a 2-chloroethyl group. Halogen-substituted alkyl groups such as bromoethyl group; hydroxy-substituted alkyl groups such as 2-hydroxyethyl group and 3-hydroxyethyl group; carboxyl-substituted alkyl groups such as carboxylmethyl group and 2-carboxyethyl group; 2-cyano group A cyano-substituted alkyl group such as an ethyl group; a 2-aminoethyl group, a 2- (N-methylamino) ethyl group;
- (N, N- dimethylamino) ethyl substituted or unsubstituted amino group-substituted alkyl group such as a group; carbamoylmethyl group, N, substituted or unsubstituted carbamoyl group substituted alkyl group, such as N- dimethylcarbamoyl ethyl group; 2-phenyl A substituted or unsubstituted aryl group-substituted alkyl group such as an ethyl group or a 2- (p-methylphenyl) ethyl group;
A substituted or unsubstituted alkoxy group-substituted alkyl group such as a methoxyethyl group or a 2-methoxyethoxy group; a substituted or unsubstituted aryloxy group-substituted alkyl group such as a 2-phenoxyethyl group or a 2- (p-methylphenoxy) ethyl group; Substituted or unsubstituted acyloxy group-substituted alkyl groups such as 2-acetoxyethyl group and 2- (p-chloro) benzoyloxyethyl group; cycloalkyloxy group-substituted alkyl groups such as cyclohexyloxymethyl group; 2-methylthioethyl group; An alkylthio-substituted alkyl group such as -ethylthiopropyl group; a phenylthiomethyl group,
A substituted or unsubstituted arylthio group-substituted alkyl group such as a 2- (p-methylphenylthio) ethyl group; a cycloalkylthio group-substituted alkyl group such as a cyclohexylthiomethyl group; 2- (2-mercaptobenzothiazolyl) ethyl A heterocyclic thio group-substituted alkyl group such as a group; a methoxycarbonylmethyl group, a 2-ethoxycarbonylethyl group,
A substituted or unsubstituted alkoxycarbonyl group-substituted alkyl group such as a 2- (2-methoxyethoxy) carbonylethyl group; a 2-phenoxycarbonylethyl group, a 2- (p-
A substituted or unsubstituted aryloxycarbonyl group-substituted alkyl group such as methoxyphenoxy) carbonylethyl group; a cycloalkyloxycarbonyl group-substituted alkyl group such as 2-cyclohexyloxycarbonylethyl group;
A carboxyl group-substituted alkyl group such as a 2-carboxyethyl group; a mercapto group-substituted alkyl group such as a 2-mercaptoethyl group;

The substituted or unsubstituted cycloalkyl group represented by X ^{1 to} X ⁸ includes those having 4 to 7 carbon atoms, such as cyclopentyl, cyclohexyl and cycloheptyl. Examples of the substituted or unsubstituted alkenyl group represented by X ^{1 to} X ⁸ include a linear or branched one having 2 to 10 carbon atoms, such as a vinyl group, an allyl group, a propenyl group, a butenyl group, and a pentenyl group. .

Examples of the substituted or unsubstituted aryl group represented by X ^{1 to} X ⁸ include a phenyl group and a naphthyl group. The substituted or unsubstituted straight-chain or branched alkyl group having 1 to 10 carbon atoms, A linear or branched alkoxy group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; and a substituted alkyl group such as a trifluoromethyl group, a hydroxyethyl group or a methoxyethyl group. and the like.

The substituted or unsubstituted heterocyclic group represented by X ^{1 to} X ⁸ includes pyridyl, quinolyl, furyl, pyranyl, pyrrolyl, imidazolyl, oxazolyl,
A pyrazolyl group, a thienyl group, a thiazolyl group, an isothiazolyl group, an isoxazolyl group, a pyrimidyl group, a triazinyl group, a benzothiazolyl group, a benzoxazolyl group, and the like. Chain alkyl group, carbon number 1-10
Linear or branched alkoxy group, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom, a trifluoromethyl group, a hydroxyethyl group, and a substituted alkyl group such as methoxyethyl group.

[0015] X ¹ methyl group as a substituent for the substituted amino group to X ^8, ethyl group, propyl group, butyl group, octyl group, 2-ethylhexyl group, dodecyl group, 2-hydroxyethyl group, 2-methoxyethyl A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms such as a group, 2- (2-methoxyethoxy) ethyl group, benzyl group, 2-phenethyl group, 2-chloroethyl group, tetrahydrofurfuryl group; vinyl group, allyl group An alkenyl group having 2 to 20 carbon atoms such as a propenyl group, a butenyl group or a pentenyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a substituted or unsubstituted aryl group having 1 to 10 carbon atoms as a substituent. linear or branched alkyl group, a linear or branched alkoxy group having 1 to 10 carbon atoms, a fluorine atom, chlorine Child, a bromine atom, a halogen atom such as iodine atom, a trifluoromethyl group, a hydroxyethyl group, those having such substituted alkyl groups such as a methoxyethyl group, specifically a phenyl group, p- chlorophenyl group, m- methyl 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, 1-substituted or unsubstituted aryl group such as a naphthyl group; a pyridyl group, a quinolyl group, a furyl group, pyranyl group, pyrrolyl group, imidazolyl group, oxazolyl group, a pyrazolyl group,
Substituted or unsubstituted heterocyclic groups 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 A substituted or unsubstituted acyl group having 1 to 20 carbon atoms such as a benzoyl group, a p-methylbenzoyl group, a 1-naphthoyl group, a thienoyl group; a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, A substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms such as -methoxyethylsulfonyl group; a phenylsulfonyl group,
substituted or unsubstituted arylsulfonyl groups 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 a benzyloxycarbonyl group; a substituted or unsubstituted aryloxycarbonyl group such as a phenyloxycarbonyl group, a p-methylphenyloxycarbonyl group or a 1-naphthyloxycarbonyl group; a cyclohexyloxycarbonyl group; And cycloalkyloxycarbonyl groups such as cyclopentyloxycarbonyl group. A substituted amino group can have one or two of these substituents. Further, the nitrogen atom of the amino group and the two substituents may be combined to form a 5- or 6-membered ring, and the ring may be a morpholine ring, a thiomorpholine ring, a piperidine ring, a piperazine ring, or the following structure ( II-a) ~ (II
Such rings -d). These rings may have a substituent.

[0016]

Embedded image X ¹ as a substituted or unsubstituted alkoxy group to X ^8, unsubstituted The alkoxy group linear or branched alkoxy group having 1 to 20 carbon atoms, specifically a methoxy group,
Ethoxy, i-propoxy, n-propoxy, i
-Butoxy group, n-butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, and the like.As the substituted alkoxy group, 20 is a the well as the number of carbon atoms of the entire substituted alkoxy group, 2-hydroxyethoxy group, 2-hydroxypropoxy group, 3-hydroxypropoxy group, a hydroxy-substituted alkoxy groups such as 4-hydroxy-butoxy group; a benzyloxy group A phenyl-substituted alkoxy group such as p-chlorobenzyloxy group or 2-phenylethoxy group;
Methoxyethoxy group, 2-ethoxyethoxy group, 2-
(N) propoxyethoxy group, 2-(iso) propoxyethoxy group, 3-methoxypropoxy group, 4-methoxybutoxy group, 3-methoxybutoxy group, 2,3-dimethoxy propoxy group, 2,2-dimethoxy-ethoxy etc. alkoxy-substituted alkoxy 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-ethylhexyl oxy) ethoxy} ethoxy group, alkoxyalkoxy substituted alkoxy group and the like; 2-phenethyloxycarbonyl ethoxy, aralkyloxy substituted alkoxy groups such as 2-benzyloxy-ethoxy; 2-acetyloxy-ethoxy An acyloxy-substituted alkoxy group such as a 2-propionyloxyethoxy group or a 2-trifluoroacetyloxyethoxy group; an alkoxycarbonyl-substituted alkoxy group such as a 2-methoxycarbonylethoxy group or a 2-ethoxycarbonylethoxy group; a furfuryloxy group; Heterocyclic-substituted alkoxy groups such as tetrahydrofurfuryloxy group; alkenyloxy-substituted alkoxy groups such as 2-allyloxyethoxy group; 2-phenoxyethoxy group and 2- (p-chlorophenoxy) ethoxy group How an aryloxy substituted alkoxy group.

[0017] X ¹ as examples of the substituted or unsubstituted cycloalkyl group having to X ⁸ in the 4 to 7 carbon atoms such as cyclopentyloxy group, cyclohexyloxy group, and the like cycloheptyl group. The substituted or unsubstituted alkenyloxy group represented by X ^{1 to} X ⁸ has 2 to 10 carbon atoms.
Linear or branched ones, for example, a vinyloxy group, an allyloxy group, a propenyloxy group, a butenyloxy group, a pentenyloxy group and the like.

The substituted or unsubstituted aryloxy group for X ^{1 to} X ⁸ includes a phenoxy group and a naphthoxy group.
Their substituent nitro group; a hydroxyl group; a mercapto group; a carboxyl group; a cyano group; a thiocyano group;
A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a linear or branched alkyl group having 1 to 10 carbon atoms; a linear or branched alkoxy group having 1 to 10 carbon atoms; a trifluoromethyl group, a hydroxyethyl group, and a substituted alkyl group such as methoxyethyl group.

The substituted or unsubstituted heterocyclic pyridyloxy groups as oxy group X ¹ to X ^8, quinolyloxy group, furyloxy group, pyranyloxy group, pillow Lil group, imidazolyloxy group, benzoxazolyl group, pyrazolyloxy group , Thienyloxy group, thiazolyloxy group, isothiazolyloxy group, isoxazolyloxy group, pyrimidyloxy group, triazinyloxy group, benzothiazolyloxy group, benzoxazolyloxy group, and the like. carbon atoms as a substituent 1 to 10
Linear or branched alkyl group having 1 to 1 carbon atoms
0 straight-chain 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 as the substituted acyloxy group acetyloxy group X ¹ to X ^8, propionyloxy group,
1-2 carbon atoms such as a butyryloxy group, an octanoyloxy group, a benzoyloxy group, a p-methylbenzoyloxy group, a 1-naphthoyloxy group and a thienoyloxy group
0. X ¹ to X ⁸ substituted or unsubstituted alkylsulfonyl methylsulfonyloxy group as group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group oxy, pentylsulfonyl group, hexylsulfonyl group, 2-ethylhexyl sulfonyl Examples thereof include those having 1 to 20 carbon atoms such as an oxy group, an n-octylsulfonyloxy group, an n-decylsulfonyloxy group, an n-dodecylsulfonyloxy group, and a 2-methoxyethoxysulfonyloxy group.

As the substituted or unsubstituted arylsulfonyloxy group for X ^{1 to} X ^8, a phenylsulfonyloxy group,
Examples thereof include a p-methylphenylsulfonyloxy group, a p-methoxyphenylsulfonyloxy group, a p-chlorophenylsulfonyl group, and a 1-naphthylsulfonyl group. Examples of the substituted or unsubstituted alkoxycarbonyloxy group for X ^{1 to} X ⁸ include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a propoxycarbonyloxy group, a butoxycarbonyloxy group, a pentyloxycarbonyloxy group, a hexyloxycarbonyloxy group, Ethylhexyloxycarbonyloxy group, n
Examples thereof include those having 1 to 20 carbon atoms such as -octyloxycarbonyloxy group, n-decyloxycarbonyloxy group, n-dodecyloxycarbonyloxy group, and 2-methoxyethoxycarbonyloxy group.

The substituted or unsubstituted aryloxycarbonyloxy group represented by X ^{1 to} X ⁸ includes a phenoxycarbonyloxy group, a p-methylphenoxycarbonyloxy group and a p-methylphenoxycarbonyloxy group.
-Methoxyphenoxycarbonyloxy group, p-chlorophenoxycarbonyloxy group, 1-naphthoxycarbonyloxy group and the like. X ^{1 to} X ^{8 as} a substituted or unsubstituted alkoxycarbonyl group, an unsubstituted alkoxycarbonyl group having 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-ethylhexyloxy Carbonyl group, n-octyloxycarbonyl group, n-decyloxycarbonyl group, n-dodecyloxycarbonyl group, and the like.Examples of the substituted alkoxycarbonyl group include
The total number of carbon atoms of the substituted alkoxy group is preferably 1 to 20, and a hydroxy-substituted alkoxycarbonyl group such as a 2-hydroxyethoxycarbonyl group, a 2-hydroxypropoxycarbonyl group, a 3-hydroxypropoxycarbonyl group, or a 4-hydroxybutoxycarbonyl group is preferred. A phenyl-substituted alkoxycarbonyl group such as a benzyloxycarbonyl group, a p-chlorobenzyloxycarbonyl group, or a 2-phenylethoxycarbonyl group; a 2-methoxyethoxycarbonyl group, a 2-ethoxyethoxycarbonyl group, or a 2- (n) propoxyethoxy group Carbonyl group, 2
-(Iso) propoxyethoxycarbonyl group, 3-methoxypropoxycarbonyl group, 4-methoxybutoxycarbonyl group, 3-methoxybutoxycarbonyl group,
2,3-dimethoxy-propoxycarbonyl group, 2,2
Alkoxy-substituted alkoxycarbonyl groups such as 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-ethylhexyloxy) ethoxy} ethoxycarbonyl group, etc .; alkoxyalkoxy-substituted alkoxycarbonyl group; 2-phenethyloxyethoxycarbonyl group;
Aralkyloxy-substituted alkoxycarbonyl groups such as 2-benzyloxyethoxycarbonyl group; acyloxy-substituted alkoxycarbonyl groups such as 2-acetyloxyethoxycarbonyl group, 2-propionyloxyethoxycarbonyl group and 2-trifluoroacetyloxyethoxycarbonyl group; - methoxycarbonyl ethoxycarbonyl group, 2-ethoxycarbonyl alkoxycarbonyl-substituted alkoxycarbonyl groups such as ethoxycarbonyl; furfuryl oxycarbonyl group, a heterocyclic-substituted alkoxycarbonyl group such as tetrahydrofurfuryl oxycarbonyl group; 2-allyl-oxy-ethoxycarbonyl alkenyloxy substituted alkoxycarbonyl group such group; 2-phenoxy ethoxycarbonyl group, 2- (p
And aryloxy-substituted alkoxycarbonyl groups such as -chlorophenoxy) ethoxycarbonyl group.

Examples of the substituted or unsubstituted cycloalkyloxycarbonyl group represented by X ^{1 to} X ⁸ include those having 4 to 7 carbon atoms, for example, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, cycloheptyloxycarbonyl group and the like. As the substituted or unsubstituted alkenyloxy group for X ^{1 to} X ^8, a linear or branched one having 2 to 10 carbon atoms, for example, vinyloxycarbonyl group, allyloxycarbonyl group, propenyloxycarbonyl group, butenyl Oxycarbonyl group, pentenyloxycarbonyl group and the like can be mentioned.

Examples of the substituted or unsubstituted aryloxycarbonyl group represented by X ^{1 to} X ⁸ include a phenoxycarbonyl group and a naphthoxycarbonyl group, and the substituents include a nitro group; a hydroxy group; a mercapto group; a carboxyl group; A thiocyano group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom;
A linear or branched alkyl group having 10 to 10 carbon atoms; a linear or branched alkoxy group having 1 to 10 carbon atoms; and a substituted alkyl group such as a trifluoromethyl group, a hydroxyethyl group, or a methoxyethyl group. No.

Examples of the substituted or unsubstituted heterocyclic oxycarbonyl group X ¹ to X ⁸ pyridyloxycarbonyl group,
Quinolylcarbonyl oxycarbonyl group, a furyl oxycarbonyl group, pyranyl oxycarbonyl group, pillow Lil oxycarbonyl group, imidazolyloxy group, benzoxazolyl oxycarbonyl group, pyrazolyloxy group, thienyl oxycarbonyl group, thiazolyl oxycarbonyl group , Isothiazolyloxycarbonyl group, isoxazolyloxycarbonyl group, pyrimidyloxycarbonyl group, triazinyloxycarbonyl group, benzothiazolyloxycarbonyl group, benzoxazolyloxycarbonyl group, and the like, the substituents as linear or branched alkyl group having 1 to 10 carbon atoms, straight-chain or branched alkoxy group having 1 to 10 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom halogen atoms, such as , Trifluoromethyl group, hydroxyethyl group, and a substituted alkyl group such as methoxyethyl group.

[0026] X1~X8 of substituted carbamoyl methyl group as a substituent group, an ethyl group, a propyl group, butyl group, octyl group, 2-ethylhexyl group, dodecyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2- (2-
Methoxyethoxy) a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms such as an ethyl group, a benzyl group, a 2-phenethyl group, a 2-chloroethyl group and a tetrahydrofurfuryl group; a vinyl group, an allyl group, a propenyl group, a 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, a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, or a linear or branched alkyl group 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. 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
A substituted or unsubstituted aryl group such as -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, a substituted or unsubstituted heterocyclic group, such as benzoxazolyl group; a formyl group, an acetyl group, a propionyl group, a butyryl group, octanoyl group, a benzoyl group, p- methylbenzoyl group, 1-naphthoyl group, a substituted or unsubstituted acyl group having 1 to 20 carbon atoms such as thienoyl group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, 2 - substituted or non-substituted alkylsulfonyl group of 1 to 20 carbon atoms, such as methoxy ethyl sulfonyl group; a phenylsulfonyl group,
substituted or unsubstituted arylsulfonyl groups 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 a benzyloxycarbonyl group; a substituted or unsubstituted aryloxycarbonyl group such as a phenyloxycarbonyl group, a p-methylphenyloxycarbonyl group or a 1-naphthyloxycarbonyl group; a cyclohexyloxycarbonyl group; And cycloalkyloxycarbonyl groups such as cyclopentyloxycarbonyl group. A substituted carbamoyl group can have one or two of these substituents. Further, the nitrogen atom of the carbamoyl group and the two substituents may be combined to form a 5- or 6-membered ring, and the ring may be a morpholine ring, a thiomorpholine ring, a piperidine ring, a piperazine ring, or the following structure ( II
-A) to (II-d), and these rings may have a substituent.

[0027]

Embedded image X ¹ methyl group as a substituent of the substituted sulfamoyl group to X ^8, ethyl group, propyl group, 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,
A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms such as a chloroethyl group and a tetrahydrofurfuryl group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group, an allyl group, a propenyl group, a butenyl group and a pentenyl group; A cycloalkyl group such as a cyclohexyl group; a substituted or unsubstituted aryl group having 1 to 1 carbon atoms as a substituent
Linear or branched alkyl group of 10, carbon atoms 1
It has 10 to 10 linear or branched alkoxy groups, halogen atoms such as fluorine, chlorine, bromine and iodine, and substituted alkyl groups such as trifluoromethyl, hydroxyethyl and methoxyethyl. what it is, specifically a phenyl group, p- chlorophenyl group, m
- methylphenyl group, p- methoxyphenyl group, p- cyanophenyl group, p- carboxyphenyl group, p- hydroxyphenyl group, p- mercaptophenyl group, p-
Substituted or unsubstituted aryl groups such as (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, a substituted or unsubstituted heterocyclic group, such as benzoxazolyl group; a formyl group, an acetyl group, a propionyl group,
C1-C20 substituted or unsubstituted acyl groups such as butyryl group, octanoyl group, benzoyl group, p-methylbenzoyl group, 1-naphthoyl group, thienoyl group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butyl A substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms such as a sulfonyl group and a 2-methoxyethylsulfonyl group; phenylsulfonyl group, p-methylphenylsulfonyl group, p-methoxyphenylsulfonyl group, p-chlorophenylsulfonyl group, 1 A substituted or unsubstituted arylsulfonyl group such as a naphthylsulfonyl group; a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group,
Substituted or unsubstituted alkoxycarbonyl group such as a benzyloxycarbonyl group; phenyloxycarbonyl group,
a substituted or unsubstituted aryloxycarbonyl group such as a p-methylphenyloxycarbonyl group and a 1-naphthyloxycarbonyl group; a cycloalkyloxycarbonyl group such as a cyclohexyloxycarbonyl group and a cyclopentyloxycarbonyl group; A substituted sulfamoyl group can have one or two of these substituents. Further, the nitrogen atom of the sulfamoyl group and 2
May be substituents, form a 5-membered or 6-membered ring together, morpholine ring as a ring, thiomorpholine ring,
Piperidine ring, piperazine ring, the following structures (II-a) to
And the rings of (II-d). These rings may have a substituent.

[0028]

Embedded image Examples of the substituted or unsubstituted acyl group of X ^{1 to} X ⁸ include a formyl group, an acetyl group, a propionyl group, a butyryl group, an octanoyl group, a benzoyl group, a p-methylbenzoyl group,
-A substituted or unsubstituted acyl group having 1 to 20 carbon atoms, such as a naphthoyl group and a thienoyl group.

The substituted or unsubstituted or unsubstituted alkylsulfonyl group represented by X ^{1 to} X ⁸ is a linear or branched alkylkisulfonyl group having 1 to 20 carbon atoms, specifically, methylsulfonyl group, ethylsulfonyl group. 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- dodecyl sulfonyl group, which halogen atom, hydroxy group, which may have a substituent such as an alkoxy group.

Examples of the substituted or unsubstituted arylsulfonyl group represented by X ^{1 to} X ⁸ include a phenylsulfonyl group and a naphthylsulfonyl group.
10 linear or branched alkyl groups, 1 carbon atom
And 10 straight-chain or branched alkoxy groups, halogen atoms such as fluorine, chlorine, bromine and iodine, and substituted alkyl groups such as trifluoromethyl, hydroxyethyl and methoxyethyl. Can be

The substituted or unsubstituted as the substituted alkylthio group linear or branched Arukirukichio group having 1 to 20 carbon atoms X ¹ to X ^8, in particular methylthio, ethylthio, i- propylthio radical, n -Propylthio group, i-
Butylthio, n- butylthio group, pentylthio group, hexylthio group, 2-ethylhexylthio group, n- octylthio group, n- decylthio group, n- etc. dodecylthio group, which halogen atom, hydroxy group, an alkoxy group May have the following substituents.

Examples of the substituted or unsubstituted cycloalkylthio group represented by X ^{1 to} X ⁸ include those having 4 to 7 carbon atoms, such as cyclopentylthio, cyclohexylthio and cycloheptylthio. Examples of the substituted or unsubstituted arylthio group represented by X ^{1 to} X ⁸ include a phenylthio group and a naphthylthio group, and the substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms and 1 to 10 carbon atoms.
Linear or branched alkoxy group, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom, a trifluoromethyl group, a hydroxyethyl group, and a substituted alkyl group such as methoxyethyl group.

Examples of the substituted or unsubstituted heterocyclic thio group represented by X ^{1 to} X ⁸ include pyridylthio, quinolylthio, furylthio, pyranylthio, pyrrolylthio, imidazolylthio, oxazolylthio, pyrazolylthio, thienylthio, and thiazolylthio. , An isothiazolylthio group, an isoxazolylthio group, a pyrimidylthio group, a triazinylthio group, a benzothiazolyl group thio, a benzooxazolylthio group, and the like. Alkyl group, linear or branched alkoxy group having 1 to 10 carbon atoms, halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, trifluoromethyl group, hydroxyethyl group, methoxyethyl group include a substituted alkyl group such as is.

[0034] As the substituted or unsubstituted alkoxysulfonyl group X ¹ to X ^8, those as the unsubstituted alkoxysulfonyl group having a linear or branched alkoxy sulfonyl group having 1 to 20 carbon atoms, specifically Are methoxysulfonyl, ethoxysulfonyl, i-propoxysulfonyl, n-propoxysulfonyl, i-butoxysulfonyl, n-butoxysulfonyl, pentyloxysulfonyl, hexyloxysulfonyl,
2-ethylhexyloxysulfonyl group, n-octyloxysulfonyl group, n-decyloxysulfonyl group,
n-dodecyloxysulfonyl group; and the substituted alkoxysulfonyl group preferably has 1 to 20 carbon atoms in terms of the total number of substituted alkoxy groups, and includes 2-hydroxyethoxysulfonyl group, 2-hydroxypropoxysulfonyl group, 3 Hydroxy-substituted alkoxysulfonyl groups such as -hydroxypropoxysulfonyl group and 4-hydroxybutoxysulfonyl group; benzyloxysulfonyl group, p-chlorobenzyloxysulfonyl group, 2
Phenyl-substituted alkoxysulfonyl groups such as -phenylethoxysulfonyl group; 2-methoxyethoxysulfonyl group, 2-ethoxyethoxysulfonyl group, 2- (n)
Propoxyethoxy sulfonyl group, 2-(iso) propoxy ethoxy sulfonyl group, 3-methoxypropoxy sulfonyl group, 4-methoxybutoxy sulfonyl group, 3
Alkoxy-substituted alkoxysulfonyl groups such as -methoxybutoxysulfonyl group, 2,3-dimethoxypropoxysulfonyl group, and 2,2-dimethoxyethoxysulfonyl group; 2- (2-methoxyethoxy) ethoxysulfonyl group, 2- (2-ethoxyethoxy) ) ethoxy sulfonyl group, 2- (2- (n) propoxyethoxy) sulfonyl group, 2- (2- (n) butoxyethoxy) ethoxy sulfonyl group, 2- {2- (2-ethylhexyl oxy)
Alkoxyalkoxy-substituted alkoxycarbonyl groups such as ethoxydiethoxysulfonyl group; aralkyloxy-substituted alkoxysulfonyl groups such as 2-phenethyloxyethoxysulfonyl group and 2-benzyloxyethoxysulfonyl group; 2-acetyloxyethoxysulfonyl group and 2-propionyl An oxyethoxysulfonyl group,
Acyloxy-substituted alkoxysulfonyl groups such as 2-trifluoroacetyloxyethoxysulfonyl group;
Alkoxycarbonyl-substituted alkoxysulfonyl groups such as methoxycarbonylethoxysulfonyl group and 2-ethoxycarbonylethoxysulfonyl group; heterocyclic-substituted alkoxysulfonyl groups such as furfuryloxysulfonyl group and tetrahydrofurfuryloxysulfonyl group;
- alkenyloxy substituted alkoxy sulfonyl group such as allyloxy ethoxysulfonyl group; 2-phenoxy-ethoxy sulfonyl group, an aryloxy-substituted alkoxy sulfonyl group, such as 2- (p-chlorophenoxy) ethoxy sulfonyl group.

The substituted or unsubstituted cycloalkyloxysulfonyl group represented by X ^{1 to} X ⁸ includes those having 4 to 7 carbon atoms, for example, cyclopentyloxysulfonyl group, cyclohexyloxysulfonyl group, cycloheptyloxysulfonyl group and the like. As the substituted or unsubstituted alkenyloxy group for X ^{1 to} X ^8, a linear or branched one having 2 to 10 carbon atoms, for example, a vinyloxysulfonyl group, an allyloxysulfonyl group, a propenyloxysulfonyl group, a butenyl Oxysulfonyl group, pentenyloxysulfonyl group and the like.

Examples of the substituted or unsubstituted aryloxysulfonyl groups represented by X ^{1 to} X ⁸ include a phenoxysulfonyl group and a naphthoxysulfonyl group, and the substituents include a nitro group; a hydroxy group; a mercapto group; a carboxyl group; A thiocyano group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom;
A linear or branched alkyl group having 10 to 10 carbon atoms; a linear or branched alkoxy group having 1 to 10 carbon atoms; and a substituted alkyl group such as a trifluoromethyl group, a hydroxyethyl group, or a methoxyethyl group. No.

As the substituted or unsubstituted heterocyclic oxysulfonyl group for X ^{1 to} X ^8, a pyridyloxysulfonyl group,
Quinolyloxysulfonyl, furyloxysulfonyl, pyranyloxysulfonyl, pyrrolyloxysulfonyl, imidazolyloxysulfonyl, oxazolyloxysulfonyl, pyrazolyloxysulfonyl, thienyloxysulfonyl, thiazolyloxysulfonyl , Isothiazolyloxysulfonyl group, isoxazolyloxysulfonyl group, pyrimidyloxysulfonyl group, triazinyloxysulfonyl group, benzothiazolyloxysulfonyl group, benzooxazolyloxysulfonyl group, and the like, As these substituents, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom Halogen sources such as , Trifluoromethyl group, hydroxyethyl group, and a substituted alkyl group such as methoxyethyl group.

Examples of the case where X ² and X ³ are bonded to each other to form a ring include those having the following structures.

[0039]

Embedded image (Wherein X ^{1 to} X ⁸ represent the same meaning as in formula (I), and X ⁹ ,
X ¹⁰ is an oxygen atom, a sulfur atom or NH, X ¹¹ is substituted or unsubstituted alkyl group, an alkenyl group, in representing) a cycloalkyl group or an aryl group, preferred ones the following general formula (IV) Is an anthraquinone compound represented

[0040]

Embedded image ^{(Wherein, Y 1, Y 4, Y} 5, Y 8 each independently represent a hydrogen atom, a nitro group, hydroxy group, a mercapto group, a halogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or Represents an unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group or a substituted or unsubstituted heterocyclic thio group,
2, Y3, Y5 and Y7 each independently represent a hydrogen atom, a hydroxy group,
Mercapto group, carboxyl group, cyano group, halogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted amino group, substituted or unsubstituted alkoxy group, substituted or unsubstituted Substituted cycloalkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group,
Substituted or unsubstituted arylsulfonyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted cycloalkyloxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, A substituted or unsubstituted acyl group, a substituted or unsubstituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkoxy sulfonyl group, a substituted or unsubstituted aryloxy sulfonyl group, Y ²
And Y ³ may combine with each other to form a ring). The compound serving as a preferred anthraquinone dye shown below.

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image The resin fine particle dispersion of the present invention can be produced by an emulsion polymerization method, a suspension polymerization method or a polymerization method such as a mini-emulsion or a micro-emulsion, but is produced by an emulsion polymerization method because of easy control of particle size distribution. Is more preferred.
To produce the resin fine particle dispersion of the present invention by an emulsion polymerization method, typically, an anthraquinone dye having a solubility in water of 0.0001 to 10 g / l and a solubility in toluene of 10 to infinity g / l. 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 thereto to carry out polymerization.

The latex resin contained in the resin particle dispersion liquid of the present invention, as monomers conventionally resin obtained by emulsion polymerization constituting the resin can be used (ethylenic monomer), preferably styrene, para Chlorostyrene, α-
Homopolymers or copolymers of styrene such as methyl styrene (styrenic resin); vinyl acetate; methyl acrylate, ethyl acrylate, n- propyl, n- butyl acrylate, lauryl acrylate, 2
Homopolymers or copolymers (vinyl 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 resins); Homopolymers or copolymers of vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether (vinyl resins); 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 Graft polymers of these non-vinyl condensation resins and vinyl monomers are exemplified.
These resins may be used alone or in combination of two or more.

Among these resins, styrene resins,
Vinyl resins, polyester resins, olefin resins are preferred, copolymers of styrene and butyl acrylate,
Particularly preferred are butyl acrylate, bisphenol A / fumaric acid copolymer, and a copolymer of styrene and olefin. In producing the resin fine particles of the present invention, the monomer and anthraquinone dye constituting the resin was emulsified in the presence of an emulsifier, and a polymerization initiator is added to the polymerization according to a standard method.

The emulsifier is selected from known cationic surfactants, anionic surfactants and nonionic surfactants, and two or more emulsifiers 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 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, and monodecanoyl. And sucrose.

[0055] The polymerization initiator is, in the case of the emulsion polymerization,
Used as water-soluble or oil-soluble. For example, potassium persulfate, sodium persulfate, ammonium persulfate alone or an initiator system constructed from a redox system thereof with an inorganic or organic salt containing iron trivalent ions, and other redox systems include hydrogen peroxide and ascorbic acid And a redox-based polymerization initiator obtained by combining the above.

[0056] The content of anthraquinone dyes, depending on the essential amount of anthraquinone dye used is usually 1-100 parts by weight per 100 parts by weight of the binder resin, it is preferably used as a 3-50 weight parts . These anthraquinone dyes are contained in polymer primary particles formed by emulsion polymerization by dissolving and using monomers dispersed in water in oil droplets in the presence of an emulsifier in the emulsion polymerization step.

In the emulsion polymerization step, considering that the anthraquinone dye moves into the micelle together with the polymer, it is better to dissolve it slightly in water, so that 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. In the emulsion polymerization step, since the colorant is preferably dissolved in oil droplets of the monomer, the solubility in toluene is preferably 5 to infinite g / l, more preferably 20 to 1000 g / l, and more preferably 30 to 300 g / l. Particularly preferred.

[0058] The volume average particle diameter of the resin fine particles is at 200nm or less, including a layer of surfactant present around the resin, preferably 120nm or less, more preferably 8
0 nm or less. When the volume average particle size is larger than the above range, self-organization is difficult to develop. The lower limit of the volume average particle size of the resin fine particles is usually 5 nm in view of the presence of the surfactant layer. However, if the volume average particle size is extremely small, the lower limit of the volume of the resin in the dispersion liquid is reduced. Since the ratio of the resin becomes too small, 10 nm or more is preferable. The average particle size, a transmission electron microscope of the resin fine particles (TE
M) (for example, Hitachi H-9000NA), and the photograph can be measured by image analysis.

The solid content concentration of the resin fine particle dispersion is usually 10 to 50%, and can be appropriately diluted according to the intended use. The anthraquinone dye-containing resin fine particle dispersion described above is obtained by dropping 0.5 ml of the resin fine particle dispersion onto 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.

[0060] In order to facilitate the expression of self-organization has a small particle size distribution, and since it is the preferred form of the particles are the same, the volume average particle diameter of the resin fine particles (DV)
Relationship between the number average particle diameter (DN) and is, 1 ≦ DV / DN ≦
1.5, preferably 1 ≦ DV / DN ≦ 1.4
Still more preferably, particularly preferably 1 ≦ DV / DN ≦ 1.3.

As a more detailed practical example, when the resin fine particles are oil-soluble dyes as anthraquinone dyes,
The resin fine particle dispersion liquid can be used as an ink for water-based paints, a printer ink capable of achieving high resolution, and the like. When the above-mentioned resin dispersion is used as a paint, 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,
Emulsions of resins such as fluororesin emulsions, rubber latex, and polyolefin resin emulsions are included. A water-miscible solvent if necessary,
Surfactants, viscosity modifiers, antioxidants, light stabilizers, ultraviolet absorbers, fungicides, anti-drying agents, etc. can be added and used. The solvent and surfactants include the same as that shown in the ink.

When the above resin dispersion is used as an ink, it can be used as an ink as it is. If necessary, a water-miscible solvent, a surfactant, a viscosity modifier, an antioxidant, light stabilizer, ultraviolet absorber, antifungal, may be used with the addition of such anti-drying agent. As the solvent, for example, 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, ethyleneuricol monoallyl ether, 2-pyrrolidone,
N-methylpyrrolidone, 1,3-dimethylimidazolidinone, thiodiethanol, sulfolane, dimethyl sulfoxide, and the like. Examples of the surfactant include known cationic surfactants, anionic surfactants, and nonionic surfactants. And two or more of them may be used in combination.

[0063] Examples of cationic surfactants are 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, And monodecanoyl sucrose.
These inks for ink jet recording, for writing instruments, can be used, such as for printing, it is suitable especially for ink jet recording.

[0065]

As the following examples, specific examples of the preparation of an anthraquinone dye containing resin particle dispersion liquid, the present invention is,
The present invention is not limited to these examples unless it exceeds the gist. [Example 1] (Preparation of anthraquinone dye-containing 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 dodecylbenzenesulfonate (S-DB
S) 12 parts of an aqueous solution and 383 parts of demineralized water were charged and heated to 90 ° C. under a nitrogen stream.

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

[0067]

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) The compound of the D-1 2 parts (aqueous emulsifier solution) 10% aqueous solution of 8 parts of sodium dodecylbenzene sulfonate demineralized water 18 parts (polymerization initiator) 8% hydrogen peroxide aqueous solution 10.6 parts 8% ascorbic acid aqueous solution 10.6 parts completion of the polymerization reaction after cooling Thus, a red polymer dispersion was obtained. The solid content concentration of the obtained polymer dispersion was 18.4%,
The yield was 92%.

[0068] As a result, the volume average particle diameter of 21 nm, D
V / DN = 1.4. A pipette was placed on recycled paper (Kokuyo Co., Ltd., product number "hi-501N") in which 0.5 ml of this resin fine particle dispersion was piled up, and allowed to stand for 5 minutes. No red color was applied to the paper, and water in the resin fine particles did not permeate the recycled paper. Example 2 (Preparation of Anthraquinone Dye-Encapsulated Resin Fine Particle Dispersion) 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 dodecyl benzene sulfonate (S-DB
S) 12 parts of an aqueous solution and 383 parts of demineralized water were charged and heated to 90 ° C. under a nitrogen stream.

Thereafter, the oil-soluble dye (the compound of D-3) was dissolved in the following monomers and dispersed in an aqueous emulsifier solution. Then, a polymerization initiator was added to the emulsion heated to 90 ° C., and emulsion polymerization was performed for 6.5 hours.

[0070]

(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 the above D-3 2 parts (Emulsifier aqueous solution) Sodium dodecylbenzenesulfonate 10% aqueous solution 8 parts Demineralized water 18 parts (Polymerization initiator) 8% aqueous hydrogen peroxide 10.6 parts 8% ascorbic acid aqueous solution 10.6 parts Thus, a blue polymer dispersion was obtained. The solid content concentration of the obtained polymer dispersion was 19.4%,
The yield was 97%.

As a result, the volume average particle diameter was 23 nm, and D
V / DN = 1.4. A pipette was placed on recycled paper (Kokuyo Co., Ltd., product number "hi-501N") in which 0.5 ml of this resin fine particle dispersion was piled up, and allowed to stand for 5 minutes. No blue color was applied to the paper, and water in the resin fine particles did not permeate the recycled paper. Example 3 (Preparation of Anthraquinone Dye-Encapsulated Resin Fine Particle Dispersion) 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 dodecylbenzenesulfonate (S-DB
S) 12 parts of an aqueous solution and 383 parts of demineralized water were charged and heated to 90 ° C. under a nitrogen stream.

Thereafter, an oil-soluble dye (the compound of D-5) was dissolved in the following monomers and dispersed in an aqueous emulsifier solution. Then, a polymerization initiator was added to the emulsion heated to 90 ° C., and emulsion polymerization was performed for 6.5 hours.

[0073]

(Table 3) (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) The compound of D-5 6 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 Thus, a yellow polymer dispersion was obtained. The solid content concentration of the obtained polymer dispersion was 17%, and the yield was 85%. The weight average molecular weight of the obtained blue resin fine particles was about 50,000.

As a result, the volume average particle diameter was 20 nm, and D
V / DN = 1.2. The resin particle dispersion 0.
Recycled paper with six 5 ml sheets (Kokuyo Co., Ltd.
01N ") with a pipette and left for 5 minutes. No bleeding, no blue coloring on the second paper from above, and water in the resin fine particles did not permeate the recycled paper. . Example 4 (Preparation of Anthraquinone Dye-Encapsulated Resin Fine Particle Dispersion) 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 dodecylbenzenesulfonate (S-DB
S) 12 parts of an aqueous solution and 383 parts of demineralized water were charged and heated to 90 ° C. under a nitrogen stream.

Thereafter, an oil-soluble dye (the compound of D-4) was dissolved in the following monomers and dispersed in an aqueous emulsifier solution. Then, a polymerization initiator was added to the emulsion heated to 90 ° C., and emulsion polymerization was performed for 6.5 hours.

[0076]

(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-4 above 10 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 Thus, a yellow polymer dispersion was obtained. The solid content concentration of the obtained polymer dispersion was 18%, and the yield was 90%. The weight average molecular weight of the resulting red resin fine particles was about 50,000.

As a result, the volume average particle diameter was 16 nm, and D
V / DN = 1.3. A pipette was placed on recycled paper (Kokuyo Co., Ltd., product number "hi-501N") in which 0.5 ml of this resin fine particle dispersion was piled up, and allowed to stand for 5 minutes. No red color was applied to the paper, and water in the resin fine particles did not permeate the recycled paper. Example 5 (Preparation of Anthraquinone Dye-Encapsulated Resin Fine Particle Dispersion) 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 dodecylbenzenesulfonate (S-DB
S) 12 parts of an aqueous solution and 383 parts of demineralized water were charged and heated to 90 ° C. under a nitrogen stream.

Thereafter, the oil-soluble dye (compound D-8) was dissolved in the following monomers and dispersed in an aqueous emulsifier solution. Then, a polymerization initiator was added to the emulsion heated to 90 ° C., and emulsion polymerization was performed for 6.5 hours.

[0079]

(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-8 2 parts (Emulsifier aqueous solution) Sodium dodecylbenzenesulfonate 10% aqueous solution 8 parts Demineralized water 18 parts (Polymerization initiator) 8% aqueous hydrogen peroxide 10.6 parts 8% ascorbic acid aqueous solution 10.6 parts Thus, a blue polymer dispersion was obtained. The solid content concentration of the obtained polymer dispersion was 13%, and the yield was 65%.

The resin microparticle dispersion (0.5 ml) was pipetted on recycled paper (Kokuyo Co., Ltd., product number “hi-501N”) in which six sheets were stacked, and was left for 5 minutes. There was no blue coloration on the second paper, and water in the resin fine particles did not permeate the recycled paper. [Example 6] (anthraquinone Preparation of dye containing resin fine particle dispersion) stirrer, heating and cooling devices, concentrator, and 10% N The following amounts of the glass reactor equipped with a respective material-assisting agent charging device
-Sodium dodecylbenzenesulfonate (S-DB
S) 12 parts of an aqueous solution and 383 parts of demineralized water were charged and heated to 90 ° C. under a nitrogen stream.

Thereafter, an oil-soluble dye (the compound of D-7) was dissolved in the following monomers and dispersed in an aqueous emulsifier solution. Then, a polymerization initiator was added to the emulsion heated to 90 ° C., and emulsion polymerization was performed for 6.5 hours.

[0082]

(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-7 2 parts (Emulsifier aqueous solution) Sodium dodecylbenzenesulfonate 10% aqueous solution 8 parts Demineralized water 18 parts (Polymerization initiator) 8% aqueous hydrogen peroxide 10.6 parts 8% ascorbic acid aqueous solution 10.6 parts to obtain a blue polymer dispersion. The solid content of the obtained polymer dispersion was 9%, the yield was 45%.

0.5 ml of the obtained resin fine particle dispersion was added to 6
Ply recycled paper placed pipetted onto (Kokuyo Co. No. "human -501N"), was allowed to stand for 5 minutes, without even without any, and the blue from above the second sheet of paper coloring from bleeding The water in the fine resin particles did not permeate the recycled paper. In Example 7 dye-containing resin fine particle dispersion prepared in Example 1 (Example of the ink preparation and evaluation)
An aqueous solution of sodium dodecylbenzenesulfonate and water are mixed, and the dye-containing resin fine particles are 10% by weight,
Sodium dodecyl benzene sulfonate was prepared so that 4% by weight. Kiriyama No.5C
(1 micron) Using a filter paper, pressure filtration was performed with nitrogen gas to obtain an ink.

[0084] put this ink to the cartridge of the ink-jet printer machine (Epson HG-4800), was printed the print test pattern on plain paper. As a result, the printed matter is,
It is excellent in color development and water resistance is as good as pigment ink,
In addition, a printed matter having excellent abrasion resistance was obtained. [Comparative Example 1] stirrer, heating and cooling devices, concentrator, and the 10% N-sodium dodecylbenzene sulfonate materials and auxiliaries following amounts glass reactor equipped with a charging device (S-DBS) aqueous solution 12 parts and 383 parts of demineralized water were charged and heated to 90 ° C. under a nitrogen stream.

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

[0086]

(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) The following compound (A) 10 Part (aqueous emulsifier solution) 10% aqueous solution of sodium dodecylbenzenesulfonate 8 parts Demineralized water 18 parts

[0087]

Embedded image (Polymerization initiator) 8% 10.6 parts during the polymerization hydrogen peroxide aqueous solution 10.6 parts 8% ascorbic acid aqueous solution, monomers phase HSR-2310 was dissolved and the solvent of the aqueous phase were phase separation. After the completion of the polymerization reaction, the mixture was cooled and the solid content of the polymer dispersion was measured. The concentration was 2% or less, so that colored fine particles containing the dye could not be prepared by emulsion polymerization.

[0088]

According to the present invention, it is possible to provide a dye-containing resin fine particle dispersion which can be applied to inks for water-based paints and printer inks capable of achieving high resolution.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 2/44 C08K 5/08 4J038 C08K 5/08 C08L 57/00 4J039 C08L 57/00 C09D 7/12 C09D 7/12 11/00 11/00 17/00 17/00 201/00 201/00 B41J 3/04 101Y (72) Inventor Akifumi Nemoto 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Corporation Yokohama Research Center Office (72) Inventor Yukichi Murata 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsubishi Research Institute of Yokohama, Ltd. house F-term (reference) 2C056 EA13 FC02 2H086 BA56 BA59 BA62 4J002 AB011 BB021 BB031 BB121 BC031 BC091 BC111 BE041 BE051 BF021 BG041 BG051 BG061 BG101 BL011 BL021 BN231 CD001 CF001 CH001 CK021 CL001 EE056 EH126 EN066 EN076 EV036 EV286 FA081 FD096 GH01 GS00 HA07 4J011 AA05 KA02 KA04 KA08 KA10 KB08 CC29 PC27 CC12 PA27 CC30 PC12 DD05 DD19 DD24 EE12 EE28 EE43 4J038 CA001 CB001 CC031 CD091 CE021 CF021 CG141 CK031 DB001 DG001 DL031 EA011 JA34 KA08 KA09 KA18 KA20 MA10 4J039 BC17 BC36 BC50 BC52 BC55 BC68 BC69 BC71 BC72 BC73 BC74 BC75

Claims (5)

[Claims] An ethylenic monomer in the presence of an anthraquinone dye represented by the following general formula (I), a surfactant, and a water-soluble polymerization initiator in water or a liquid mainly containing water: the a resin particle obtainable by emulsion polymerization, resin particles, characterized in that the anthraquinone dye is 0.1% or more in the resin particles. Embedded image (Wherein X ^{1 to} X ⁸ each independently represent a hydrogen atom, a nitro group, a hydroxy group, a mercapto group, a carboxyl group, a 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 an unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted Substituted alkylsulfonyloxy group, substituted or unsubstituted arylsulfonyloxy group, substituted or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted aryloxycarbonyloxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted cycloalkyloxy group Bonyl 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, 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, substituted or unsubstituted heterocyclic oxysulfonyl group Represents Le group, X
² and X ³ may be bonded to each other to form a ring). 2. A volume average particle size (DV) of 5 nm or more and 20 or more.
And at 0nm less, and the relationship between the volume average particle diameter and (DV) to a number average particle diameter (DN) is, 1 ≦ DV / DN ≦ 1.5
2. The resin fine particles according to claim 1, wherein 3. A process according to claim 1 or 2 of the resin fine particles is emulsified dispersed in a liquid mainly comprising water or a water dispersion liquid of resin fine particles. An ink using the resin fine particle dispersion according to any one of claims 1 to 3. 5. A paint using the resin particle dispersion liquid according to claims 1 to 3.