JP2002220477A - Production method for colored resin particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method for colored resin particle that forms a film good in dispersibility of a pigment and excellent in sharpness of color and transparency. SOLUTION: A coloring agent (B) and an organic solvent (D) are mixed to be 1-50 wt.% in a concentration of a solid content, and thereafter this coloring agent is dispersed in the organic solvent using a high-pressure spray-nozzle type dispersing apparatus or a ultrasonic dispersing apparatus. A prepolymer (A-1) having a reactive group that is a precursor of a resin (A), is dissolved or dispersed in the above dispersed solution to be 20-95 wt.% in the concentration of the solid content. This dissolved or dispersed solution is emulsified or dispersed in an aqueous solvent, and, (A-1) is extended and/or cross-linked by an extending agent and/or a cross-linking agent (A-2) to form the resin (A). This resin (A) is granulated to give the colored resin particle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing colored resin particles which form a coating film having good dispersibility of a pigment and excellent color sharpness and transparency. For more information,
For powder coatings with excellent heat melting property and powder fluidity, resin for hot melt molding, spacers for manufacturing electronic parts such as liquid crystal, standard particles for electronic measurement equipment, electrophotography, electrostatic recording, electrostatic printing, etc. The present invention relates to a method for producing colored resin particles useful for a toner used and other molding materials.

[0002]

2. Description of the Related Art Conventionally, resin particles obtained by a method of emulsifying and dispersing a resin or a solvent solution of a resin in an aqueous medium or an organic solvent medium to obtain a resin particle dispersion, and then removing the medium. Means that fine particles with high sphericity can be easily obtained by adjusting the shearing force applied to the system during emulsification / dispersion and controlling the surface tension by adding a surfactant, a polymer protective colloid, etc. From
Widely applied to powder coatings, resin powder for hot-melt molding, spacers for manufacturing electronic components such as liquid crystals, standard particles for electronic measurement equipment, toner used for electrophotography, electrostatic recording, electrostatic printing, etc. I have. Powder paint, electrophotography, electrostatic recording,
When a pigment or the like is dispersed to color particles for designing as a toner or the like used for electrostatic printing or the like, it is necessary to crush the pigment to primary particles and uniformly disperse the pigment in the resin. If the dispersion of the pigment is non-uniform in the resin, or if there are many secondary particles in which the primary particles of the pigment are agglomerated, the color sharpness of the coating film,
There are problems such as deterioration of transparency. In order to solve such a problem, it has been proposed to improve the dispersibility of a pigment in a resin or a solvent solution of a resin emulsified and dispersed in an aqueous medium or an organic solvent medium, and JP-A-2-153361.
In the publication, as a method for producing a dry toner, a pigment is dispersed in a resin by melt-kneading, and then dissolved in a solvent to prepare a toner preparation liquid. There is disclosed a method for obtaining resin particles containing a pigment by volatilization. This method has good pigment dispersibility immediately after melt-kneading. However, when this melt-kneaded product is dissolved in a solvent, secondary agglomeration of the pigment occurs. Therefore, the pigment dispersibility of the obtained resin particles is not necessarily good. In addition, there is a problem that the color sharpness and transparency of the coating film are inferior.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances in the prior art. That is, it is an object of the present invention to provide colored resin particles having good pigment dispersibility and excellent color sharpness and transparency.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have obtained industrially colored resin particles having good pigment dispersibility and excellent color sharpness and transparency of a coating film. Thus, the present inventors have found a method for obtaining the efficiency more efficiently, and have reached the present invention.
That is, the present invention provides a colorant (B) and an organic solvent (D)
Is mixed so as to have a solid concentration of 1 to 50% by weight, and then the colorant is dispersed in an organic solvent using a high-pressure injection nozzle type disperser or an ultrasonic disperser, and the resin (A) is added to the dispersion. The reactive group-containing prepolymer (A-1), which is a precursor of (A), is dissolved or dispersed so as to have a solid concentration of 20 to 95% by weight, and the dissolved or dispersed liquid is emulsified or dispersed in an aqueous medium. And an elongating agent and / or a crosslinking agent (A-
This is a method for producing colored resin particles, wherein the resin (A) is formed by elongating and / or cross-linking (A-1) according to 2), followed by granulation.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The resin (A) in the present invention is a reactive group-containing prepolymer (A-
It is a reaction product of 1) and an extender and / or a crosslinking agent (A-2). Examples of the combination of the reactive group of the reactive group-containing prepolymer (A-1) and the extender and / or the crosslinking agent (A-2) include the following. : The reactive group of (A-1) is a functional group (A-1-1) capable of reacting with an active hydrogen compound;
Is a combination of the active hydrogen compound (A-2-1). : The reactive group of (A-1) is an active hydrogen-containing group (A
-1-2), wherein (A-2) is a compound (A-2-2) capable of reacting with an active hydrogen-containing group.

In the above, examples of the functional group (A-1-1) capable of reacting with an active hydrogen compound include an isocyanate group, a blocked isocyanate group, an epoxy group, an acid anhydride group and an acid halide group. Preferred among these are isocyanate groups, blocked isocyanate groups and epoxy groups. Examples of the blocked isocyanate group include those obtained by blocking an isocyanate group with a phenol derivative, oxime, caprolactam, or the like.

The active hydrogen compound (A-2-1) includes
Examples thereof include polyamines (1), polyamines that may be blocked with a removable compound, polyols (2), polymercaptans, and water. Of these, preferred are polyamines (1), polyamines which may be blocked with a removable compound, polyols and water.

The polyamines (1) include aliphatic polyamines (C2 to C18): aliphatic polyamines {C2 to
C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, Tetraethylenepentamine, pentaethylenehexamine, etc.]; these alkyl (C1 -C4) or hydroxyalkyl (C
2-C4) substituted [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-
Hexamethylenediamine, methyliminobispropylamine, etc.]; alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,
10-tetraoxaspiro [5,5] undecane, etc.]; aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamines (C4 to C15) : 1,3-
Heterocyclic polyamines (C4 to C15) such as diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline): piperazine, N-aminoethylpiperazine, 1,4- Diaminoethylpiperazine, 1,4
Aromatic polyamines (C6-C20) such as bis (2-amino-2-methylpropyl) piperazine: unsubstituted aromatic polyamines [1,2-, 1,3- and 1,4-phenylenediamine, 2,4 '-And 4,4'-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m- Aminobenzylamine, triphenylmethane-4,4 ', 4 "-triamine, naphthylenediamine and the like; a nucleus-substituted alkyl group [methyl, ethyl, n-
And C1-C4 alkyl groups such as i-propyl, butyl and the like), for example, 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4'-diamino −
3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-diethyl-2,4- Diaminobenzene,
1,3-dimethyl-2,6-diaminobenzene, 1,4
-Diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl -2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,
4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl-1,
4-diaminonaphthalene, 2,6-dimethyl-1,5-
Diaminonaphthalene, 2,6-diisopropyl-1,5
-Diaminonaphthalene, 2,6-dibutyl-1,5-diaminonaphthalene, 3,3 ', 5,5'-tetramethylbenzidine, 3,3', 5,5'-tetraisopropylbenzidine, 3,3 ', 5,5'-tetramethyl-4,
4'-diaminodiphenylmethane, 3,3 ', 5,5'
-Tetraethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraisopropyl-4,4
'-Diaminodiphenylmethane, 3,3', 5,5'-
Tetrabutyl-4,4'-diaminodiphenylmethane,
3,5-diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,5-diisopropyl-3'-methyl-2', 4-diaminodiphenylmethane, 3,3 '
-Diethyl-2,2'-diaminodiphenylmethane,
4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-
Diaminobenzophenone, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminobenzophenone,
3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3', 5,5'-tetraisopropyl-4,4'-diaminodiphenylsulfone, etc.] Mixtures of various proportions;
Aromatic polyamines having a nucleus-substituted electron withdrawing group (halogen such as Cl, Br, I and F; alkoxy group such as methoxy and ethoxy; nitro group) [methylenebis-o-
Chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1 4,4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4′-
Diamino-3,3'-dimethyl-5,5'-dibromo-
Diphenylmethane, 3,3'-dichlorobenzidine,
3,3'-dimethoxybenzidine, bis (4-amino-
3-chlorophenyl) oxide, bis (4-amino-2)
-Chlorophenyl) propane, bis (4-amino-2-
Chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl)
Sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulphide, 4,4'-methylenebis (2-iodoaniline), 4,4 ' -Methylenebis (2-bromoaniline), 4,4'-methylenebis (2-fluoroaniline), 4-aminophenyl-2
-Chloroaniline and the like]; aromatic polyamine having a secondary amino group [-NH of the above aromatic polyamine]
2 wherein part or all of 2 is replaced by -NH-R '(R' is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4'-di (methylamino) diphenylmethane, 1- Methyl-2-methylamino-4-aminobenzene, etc.), polyamide polyamines: dicarboxylic acids (such as dimer acids) and excess (more than 2 moles per mole of acid) polyamines (such as the above-mentioned alkylenediamines and polyalkylene polyamines) And polyetherpolyamines: hydrides of cyanoethylated polyether polyols (such as polyalkylene glycols) such as low molecular weight polyamide polyamines obtained by condensation of

The polyamines which may be blocked with a removable compound include the polyamines (1)
And ketones having 3 to 8 carbon atoms (e.g., acetone, methyl ethyl ketone, and methyl isobutyl ketone).

The polyols include diols (2) and polyols having three or more valences (3). Among these, diol (2) alone or a mixture of diol (2) and a small amount of trivalent or higher polyol (3) is preferable.
As the diol (2), alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,
3-propylene glycol, 1,4-butanediol,
1,6-hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, etc.); alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.);
Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S
And the like. An alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol; and an alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above bisphenols are mentioned. Of these, preferred are those having 2 to 1 carbon atoms.
And alkylene oxide adducts of bisphenols. Particularly preferred are alkylene oxide adducts of bisphenols and combinations of these with alkylene glycols having 2 to 12 carbon atoms. As the trivalent or higher polyol (3),
Octahydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane,
Pentaerythritol, sorbitol, etc.); trisphenols (trisphenol PA, etc.); novolak resins (phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trisphenols; alkylene oxide adducts of the above novolak resins. . Preferred of these are:
An alkylene oxide adduct of a polyhydric aliphatic alcohol having 3 to 8 or more valences and a novolak resin,
Particularly preferred are alkylene oxide adducts of novolak resins. As the polymercaptans, ethylenedithiol, 1,4-butanedithiol, 1,6-
Hexanedithiol and the like. Further, if necessary, a reaction terminator can be used together with (A-2-1). Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.); those obtained by blocking monoamines (eg, ketimine compounds); monools (methanol, ethanol, isopropanol, butanol, phenol; monomercaptan (butyl mercaptan, Lauryl mercaptan, etc.)
And the like.

The above-mentioned prepolymer (A-1)
Examples of the active hydrogen-containing group (A-1-2) include an amino group, a hydroxyl group (an alcoholic hydroxyl group and a phenolic hydroxyl group), a mercapto group, a carboxyl group, and an organic group blocked with a compound capable of leaving them. And the like. Among these, preferred are an amino group and a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group).
And an organic group in which an amino group is blocked by a compound capable of leaving. Examples of the organic group blocked with a compound from which an amino group can be eliminated include a ketimine group and an oxazoline group obtained by dehydrating and condensing an amino group with ketones (such as acetone, methyl ethyl ketone, and methyl isobutyl ketone).

A compound capable of reacting with an active hydrogen-containing group (A-
Examples of 2-2) include polyisocyanates (4), polyepoxides (5), polycarboxylic acids, polyacid anhydrides, and polyacid halides. Among these, preferred are polyisocyanates (4),
And polyepoxides (5).

The polyisocyanates (4) include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter), aliphatic polyisocyanates having 2 to 18 carbon atoms, and 4 to 4 carbon atoms. 15 alicyclic polyisocyanates, araliphatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretoimine group, Isocyanurate group, oxazolidone group-containing modified product) and a mixture of two or more of these.
Specific examples of the aromatic polyisocyanate include 1,
3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or
Or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; Mixture with trifunctional or higher polyamine]: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, m- and p-isocyanate Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and dodecamethylene diisocyanate. 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6
-Diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,
Aliphatic polyisocyanates such as 6-diisocyanatohexanoate; Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-
Diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl)
-4-cyclohexene-1,2-dicarboxylate,
2,5- and / or 2,6-norbornane diisocyanate. Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′,
α'-tetramethylxylylene diisocyanate (TM
XDI). The modified polyisocyanate includes modified MDI (urethane-modified MDI,
Carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified products of polyisocyanates such as urethane-modified TDI, and mixtures of two or more of these [for example, a combination of modified MDI with urethane-modified TDI (isocyanate-containing prepolymer)]. It is.
Among these, preferred are aromatic polyisocyanates having 6 to 15 atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HD
I, hydrogenated MDI, and IPDI.

The polyepoxides (5) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compound include glycidyl ethers and glycidyl esters of polyhydric phenols, glycidyl aromatic polyamines, and glycidylated aminophenols. Examples of glycidyl ethers of polyhydric phenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4 '
-Dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, dihydroxynaphthyl cresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolyl bisphenol A glycidyl ether, trismethyl-tret-butyl-butylhydroxymethanetriglycidyl ether, 9,9′-bis (4-hydroxyphenyl) fluoro orange glycidyl ether, 4,4′-oxybis (1 , 4-phenylethyl) tetracresol glycidyl ether, 4,4'-oxybis (1,4-
Phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, glycidyl ether of phenol or cresol novolak resin, glycidyl ether of limonenephenol novolak resin, obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin Examples thereof include a diglycidyl ether, a polyglycidyl ether of polyphenol obtained by a condensation reaction of phenol and glyoxal, glutaraldehyde, or formaldehyde, and a polyglycidyl ether of polyphenol obtained by a condensation reaction of resorcinol and acetone. Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate. As the glycidyl aromatic polyamine, N, N-diglycidylaniline, N, N, N ′,
N'-tetraglycidylxylylenediamine, N, N,
N ', N'-tetraglycidyldiphenylmethanediamine and the like. Further, in the present invention, as the aromatic system, a triglycidyl ether of P-aminophenol, a diglycidyl urethane compound obtained by an addition reaction of tolylene diisocyanate or diphenylmethane diisocyanate with glycidol, and a polyol obtained by reacting the two reactants with a polyol. And a diglycidyl ether of an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A. Heterocyclic polyepoxy compounds include trisglycidyl melamine; alicyclic polyepoxy compounds include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) Ether, ethylene glycol bisepoxy dicyclopentyl ale,
3,4-epoxy-6-methylcyclohexylmethyl-
3 ′, 4′-Epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,3
4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester, and the like. The alicyclic compound also includes a nuclear hydrogenated product of the aromatic polyepoxide compound. The aliphatic polyepoxy compound includes a polyglycidyl ether of a polyhydric aliphatic alcohol and a polyglycidyl ester of a polyhydric fatty acid. And glycidyl fatty amines. Examples of polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol. Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, etc. Is mentioned. Examples of polyglycidyl esters of polyvalent fatty acids include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimerate, and the like. Glycidyl aliphatic amines include N, N, N ', N'-tetraglycidylhexamethylenediamine. In the present invention, the aliphatic system also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, aliphatic polyepoxy compounds and aromatic polyepoxy compounds are preferred.

Examples of the polycarboxylic acids include dicarboxylic acids (6), tricarboxylic or higher polycarboxylic acids (7), and acid anhydrides thereof. Examples of the dicarboxylic acid (6) include alkylenedicarboxylic acids (succinic acid, adipic acid, sebacic acid, dodecenylsuccinic acid, azelaic acid,
Sebacic acid, dodecane dicarboxylic acid, octadecane dicarboxylic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); Acid, octadecenylsuccinic acid, etc.), alkyl succinic acids (decylsuccinic acid, dodecylsuccinic acid, octadecylsuccinic acid, etc.);
Aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) and the like can be mentioned. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Trivalent or higher polycarboxylic acid (7)
Examples thereof include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).

Examples of the polycarboxylic anhydride include maleic anhydride, phthalic anhydride, pyromellitic anhydride and the like. Examples of the polyacid halides include the above-mentioned acid halides (acid chloride, acid bromide, acid iodide). Further, if necessary, a reaction terminator can be used together with (A-2-2). As the reaction terminator, monoisocyanates (lauryl isocyanate,
Phenylisocyanate, etc.), monoepoxide (butyl glycidyl ether, etc.), monoamine (diethylamine, dibutylamine, butylamine, laurylamine, etc.); monoamine blocked (ketimine compound, etc.); monool (methanol, ethanol, isopropanol, butanol, Phenol; monomercaptan (butyl mercaptan, lauryl mercaptan, etc.) and the like.

The equivalent ratio of the reactive group in the reactive group-containing prepolymer (A-1) to the active hydrogen-containing group in (A-2) is as follows:
Usually 1/2 to 2/1, preferably 1.5 / 1 to 1/1.
5, more preferably 1.2 / 1 to 1 / 1.2.
When (A-2) is water, water is handled as a divalent active hydrogen compound.

The prepolymer (A-1) includes prepolymers such as polyester, epoxy resin, polyurea resin and polyurethane. Examples of the polyester include a polycondensate of a polyol with a polycarboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof. As the polyol, the diol (2) and the tri- or higher valent polyol (3) are used. (7) and their acid anhydrides or lower alkyl esters, and the preferred ones are also the same. The ratio of the polyol to the polycarboxylic acid is usually 2/1 to 1/1, preferably 1.5 / 1 to 1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH].
/ 1, more preferably from 1.3 / 1 to 1.02 / 1. The polyester is prepared by converting a polycarboxylic acid and a polyol to 150 to 280 in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide.
It is obtained by heating to ° C. and performing dehydration condensation. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.

As the epoxy resin, the above-mentioned polyepoxides (5) and the above-mentioned active hydrogen compound (D) ｛water, polyol [the above-mentioned diol (2) and tri- or higher valent polyol (3)], dicarboxylic acid (6) Polycarboxylic acid (7) having a valency of 3 or more, polyamine (1), etc., and polyadducts of dicarboxylic acid (6) or polycarboxylic acid (7) having a valency of 3 or more with acid anhydride; The same applies to preferred ones.

As the polyurethane, the polyisocyanate (4) and the active hydrogen compound (D) 水 素 water, a polyol [the diol (2) and the polyol having a valence of 3 or more (3)], dicarboxylic acids (6), Or higher polyvalent polycarboxylic acids (7), polyamines (1), and the like, and polyadducts thereof, and the like are preferable.

The method for incorporating a reactive group into a polyester, an epoxy resin, a polyurethane or the like includes: a method in which a functional group of a component is left at an end by using one of the components in excess; And a method of reacting a compound containing a reactive group with a reactive group.

In the method described above, a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, and an isocyanate A group-containing polyurethane prepolymer is obtained. For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the polyol to the polycarboxylic acid is such that the ratio of the hydroxyl group [OH] to the carboxyl group [C
The molar ratio [OH] / [COOH] of OOH] is usually 2 /
The ratio is from 1/1 to 1, preferably from 1.5 / 1 to 1/1, and more preferably from 1.3 / 1 to 1.02 / 1. In the case of other constituent components and terminal prepolymers, the ratios are the same except that the constituent components are changed.

The prepolymer obtained in the above method is reacted with a polyisocyanate to obtain an isocyanate group-containing prepolymer, and the blocked polyisocyanate is reacted to obtain a blocked isocyanate group-containing prepolymer. An epoxy group-containing prepolymer is obtained by reacting the polyepoxide,
By reacting the polyanhydride, an acid anhydride group-containing prepolymer is obtained. Examples of the polyisocyanate include those similar to the above-mentioned polyisocyanates (4), and preferred ones are also the same.

The ratio of the compound containing a reactive group is, for example, when a polyisocyanate is reacted with a hydroxyl group-containing polyester to obtain an isocyanate group-containing polyester prepolymer, the ratio of the polyisocyanate is isocyanate group [NCO] Hydroxyl group of polyester
The molar ratio of [OH] [NCO] / [OH] is usually 5/1 to 1
The ratio is 1/1, preferably 4/1 to 1.2 / 1, and more preferably 2.5 / 1 to 1.5 / 1. In the case of other constituent components and terminal prepolymers, the ratios are the same except that the constituent components are changed.

The content of the reactive group in the prepolymer (A-1) is usually from 150 to 30,000, preferably from 300 to 20, in terms of the number average molecular weight of the prepolymer / the number of reactive groups.
000. The number average molecular weight of (A-1) is usually 50
0 to 30,000, preferably 1,000 to 20,000
0, and more preferably 2,000 to 10,000. The weight average molecular weight of (A-1) is 1,000 to 5
000, preferably 2,000 to 40,000, more preferably 4,000 to 20,000.

Further, if necessary, a reaction terminator can be used together with (A-2). Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

The extension and / or crosslinking reaction time is selected depending on the reactivity of the combination of the reactive group structure of the prepolymer (A-1) and the extender and / or the crosslinking agent (A-2). It is usually from 10 minutes to 40 hours, preferably from 2 to 24 hours. The reaction temperature is usually from 0 to 15
0 ° C., preferably 50 to 120 ° C. In addition, a known catalyst can be used as needed. Specifically, for example, in the case of the reaction of isocyanate, dibutyltin laurate, dioctyltin laurate and the like can be mentioned.

In the present invention, (A-1) and (A-2)
The glass transition point (Tg), molecular weight, SP value, and molecular weight between cross-linking points of a resin produced by elongation and / or cross-linking reaction vary in a preferable range depending on the application, and may be appropriately adjusted.

As the colorant (B) in the present invention, white pigments, yellow pigments, orange pigments, red pigments, purple pigments,
Blue pigment, green pigment, brown pigment, black pigment and the like can be mentioned. Each of the above-mentioned pigments includes an inorganic pigment and an organic pigment. Specific examples of the inorganic pigment include titanium oxide, carbon black, chromium oxide, ferrite, red iron, navy blue, and the like.

Specific examples of carbon black include carbon black # 2400 and # 2350 manufactured by Mitsubishi Chemical Corporation.
# 2300, # 2200, # 1000, # 980, # 9
70, # 960, # 950, # 900, # 850, # 6
50, # 4000, # 4010, # 55, # 52, # 4
7, # 45, # 44, # 40, # 33, # 32, # 3
0, # 20, # 10, # 5, # 3050, # 3150,
# 3250, # 3750, # 3950, MCF88, M
A600, MA7, MA8, MA11, MA100, M
A220, IL30B, IL31B, IL7B, IL1
1B, IL52B, CF9, Diamond Black A, N22
0M, 234, I, LI, II, N339, SH, SH
A, LH, HA, SF, N550M, E, G, R, G
(Both are trade names). Among these carbon blacks, carbon blacks having a pH of 2 to 9 are preferred from the viewpoint of dispersion stability. The carbon black may be subjected to a surface treatment for the purpose of improving functions such as dispersibility, hydrophobicity and hydrophilicity. Examples of the surface treatment method include polymer grafting, surface oxidation treatment, surface adsorption treatment with wax, surfactant and the like. These can be performed by a known method.

As organic pigments, phthalocyanine pigments,
Azo lake type, mono azo type, disazo type, condensed azo type,
Chelate azo, quinacridone, dioxazine, isoindolinone, thioindigo, perylene, quinophthalone, anthraquinone, carmine, naphthol, pyrazolone, dibromoanthrone and the like.

The following are specific examples of the organic pigment. [Displayed by color index (CI) number] Yellow pigment: CI Pigment Yellow 11, 20, 24, 3
1, 53, 83, 86, 93, 99, 108, 109,
110, 117, 125, 129, 137, 138, 1
39, 147, 148, 150, 151, 153, 15
4, 166, 167, 168 Orange pigment: CI Pigment Orange 36, 38, 43, 5
1, 55, 59, 61 Red pigment: CI Pigment Red 9, 97, 105, 12
2, 123, 149, 150, 155, 168, 17
1, 175, 176, 177, 180, 192, 20
9, 215, 216, 217, 220, 223, 22
4, 226, 227, 228, 240 Purple pigment: CI Pigment Violet 19, 23, 29, 3
0, 32, 37, 39, 40, 50 Blue pigment: CI Pigment Blue 1, 2, 15, 15:
3, 15: 4, 15: 6, 22, 60, 64, 66 Green pigment: CI Pigment Green 7, 36, 37 Brown pigment: CI Pigment Brown 23, 25, 26, 28 Black pigment: CI Pigment Black 1, 7 The type of pigment used is The preferred system differs depending on the application, the use and the composition of the resin (A), and may be appropriately selected. Organic pigments that have been subjected to surface treatment for the purpose of improving functions such as dispersibility, hydrophobicity, and hydrophilicity may be used. Examples of the surface treatment method include polymer grafting, surface oxidation treatment, surface adsorption treatment with wax, surfactant and the like. These can be performed by a known method.

As the other resin (C) in the present invention, any resin can be used as long as it is used as necessary and known resins. Polyethylene, polypropylene, polystyrene, styrene-alkyl (meth) acrylate copolymer, styrene-butadiene copolymer, acrylic acid-alkyl acrylate copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer As polycondensation resins, polyester resins, polyamide resins, polyimide resins, polycarbonate resins, silicon resins; as polyaddition resins, polyurethane resins, polyurea resins, epoxy resins; as addition polymerization resins,
Phenol resins, melamine resins, aniline resins; examples of other resins include unsaturated polyester resins and ionomer resins. Of these, vinyl resins, polyester resins, polyurethane resins, polyurea resins and epoxy resins are preferred.

The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. Examples of the vinyl monomer include the following (1) to (13).

(1) Vinyl hydrocarbon: (1) -1) Aliphatic vinyl hydrocarbon: alkenes having 2 to 20 carbon atoms, for example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene , Dodecene, octadecene, other α-olefins and the like; alkadienes having 4 to 20 carbon atoms, such as butadiene, isoprene, 1,4-pentadiene, 1,6
-Hexadiene, 1,7-octadiene. (1) -2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidene bicycloheptene, etc .; terpenes,
For example, pinene, limonene, indene and the like. (1) -3) Aromatic vinyl hydrocarbon: styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted product, for example, α-
Methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, and the like; and Vinyl naphthalene.

(2) a carboxyl group-containing vinyl monomer and a salt thereof: an unsaturated monocarboxylic acid having 3 to 30 carbon atoms;
Unsaturated dicarboxylic acids and their anhydrides and their monoalkyl (C1-24) esters, for example (meth)
Acrylic acid, maleic anhydride, monoalkyl maleate, fumaric acid, monoalkyl fumarate, crotonic acid, itaconic acid, monoalkyl itaconic acid, glycol monoether itaconate, citraconic acid, monoalkyl citraconic acid And carboxyl group-containing vinyl monomers such as cinnamic acid.

(3) Sulfone group-containing vinyl monomers, vinyl sulfate monoesters and salts thereof: 2 carbon atoms
To 14 alkenesulfonic acids such as vinylsulfonic acid, (meth) allylsulfonic acid, methylvinylsulfonic acid, and styrenesulfonic acid; and alkyl derivatives having 2 to 24 carbon atoms such as α-methylstyrenesulfonic acid; (Hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, for example, sulfopropyl (meth) acrylate, 2-hydroxy-3-
(Meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfone Acid, 2- (meth) acrylamide-
2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (3 to 18 carbon atoms) allyl sulfosuccinic acid, poly (n =
2-30) oxyalkylene (ethylene, propylene,
Butylene: Sulfate of mono (meth) acrylate [poly (n = 5)
15) Oxypropylene monomethacrylate sulfate] and polyoxyethylene polycyclic phenyl ether sulfate; and salts thereof.

(4) Phosphoric acid group-containing vinyl monomers and salts thereof: (meth) acryloyloxyalkyl (C1-C2
4) Phosphoric acid monoesters, for example, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) phosphonic acids,
For example, 2-acryloyloxyethyl phosphonic acid

The salts (2) to (4) include, for example, alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (calcium salt, magnesium salt, etc.), ammonium salt, amine salt and Secondary ammonium salts.

(5) Hydroxyl group-containing vinyl monomers: hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene- 1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether,
Sucrose allyl ether, etc.

(6) Nitrogen-containing vinyl monomer: (6) -1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butyl Aminoethyl methacrylate, N
-Aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4
-Vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetoaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole , Aminopyrrole, aminoimidazole, aminomercaptothiazole, salts thereof, etc. (6) -2) Amide group-containing vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N
-Butyl acrylamide, diacetone acrylamide,
N-methylol (meth) acrylamide, N, N'-methylene-bis (meth) acrylamide, cinnamamide,
N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc. (6) -3) Nitrile group-containing vinyl monomer: (meth)
Acrylonitrile, cyanostyrene, cyanoacrylate, etc. (6) -4) Quaternary ammonium cation group-containing vinyl monomer: dimethylaminoethyl (meth) acrylate,
3 such as diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine, etc.
(6) -5) Nitro group-containing vinyl monomer (a quaternized product of a tertiary amine group-containing vinyl monomer (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, or dimethyl carbonate)) : Nitrostyrene, etc.

(7) Epoxy group-containing vinyl monomers: glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc.

(8) Vinyl monomer containing halogen element:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, etc.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones: (9) -1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate , Isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxy acetate, vinyl benzoate, ethyl α
-Ethoxy acrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups having 2 to 8 carbon atoms, A branched or alicyclic group), dialkyl maleate (two alkyl groups are a straight, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) Allyloxyalkanes [diaryloxyethane, triaryloxyethane, tetraallyloxyethane Emissions, tetra allyloxy propane, tetra Ali Loki Shiv Tan, tetra meth allyloxy ethane], and the like, polyalkylene glycol chain vinyl monomers [polyethylene glycol having a (molecular weight 30
0) Mono (meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate, etc.), poly (meth) acrylate [Poly (meth) acrylates of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (9) -2) vinyl (thio) ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, Vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2
-Butoxyethyl ether, 3,4-dihydro-1,2-
Pyran, 2-butoxy-2'-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, (9) -3) vinyl ketone, for example, vinyl methyl ketone,
Vinyl ethyl ketone, vinyl phenyl ketone; vinyl sulfone such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide and the like.

(10) Other vinyl monomers: isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, etc.

Examples of the copolymer of a vinyl monomer include a polymer obtained by copolymerizing any of the above-mentioned monomers (1) to (10) in a binary number or more in an arbitrary ratio.

The vinyl resin can be synthesized by a known polymerization method such as suspension, emulsification, and solution polymerization of the above-mentioned monomer using a radical polymerization catalyst. The polymerization temperature is usually 10 to 2
The reaction temperature is usually 00C, preferably 40C to 180C, and the reaction time is usually 1 48 hours, preferably 4 24 hours. Examples of the radical polymerization catalyst include azo catalysts: azoisobutyronitrile, azoisodimethylvaleronitrile, peroxide catalysts: t-butyl peroxide, cumyl peroxide, etc., and persulfate catalysts: sodium persulfate, peroxide Ammonium sulfate, potassium persulfate, or the like can be used. A polymerization solvent may be used during the reaction, and toluene, xylene, ethyl acetate, butyl acetate,
Acetone, methyl ethyl ketone, methyl isobutyl ketone, ethanol, isopropanol and the like can be used.

Examples of the polyester resin include the same ones as described above, and preferred ones are also the same.

Examples of the polyurethane resin include the same ones as described above, and preferred ones are also the same.

Examples of the polyurea resin include a reaction product of the above-mentioned polyisocyanates (4) and amines (1).

Examples of the epoxy resin include the same ones as described above, and preferred ones are also the same.

Organic solvent (D) used in the present invention
The boiling point is usually 50 to 150 ° C., preferably 50 to 150 ° C.
~ 120 ° C, specifically, n-hexane,
It is n-octane, toluene, xylene, ethyl acetate, n-butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethylformamide or a mixed solvent of two or more thereof. Among these, preferred organic solvents are toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone and tetrahydrofuran, and particularly preferred are toluene, ethyl acetate, acetone, methyl ethyl ketone and tetrahydrofuran.

In the present invention, the colorant (B) is mixed with an organic solvent and then dispersed in the organic solvent using a high-pressure jet nozzle type disperser or an ultrasonic type disperser. The high-pressure jet nozzle type disperser applies a high pressure to the liquid processing material to allow it to pass through a very narrow flow path at a high speed, suddenly bend the flow path at a right angle, or suddenly diffuse, and hit the barrier plate. This is a device that applies high-density energy due to cavitation and collision to a liquid processed material to perform dispersion and emulsification.
Ultrasonic dispersing machines are devices that apply high pressure to a liquid processing object, eject it at high speed from an orifice, and impinge on the blade, causing the blade to emit self-excited light, which causes cavitation and dispersion of the liquid processing object. There is a device that vibrates an ultrasonic vibrator connected to a sound wave transmitter at a high frequency in an irradiation cell and applies ultrasonic waves to a liquid processing object sent into the cell to disperse the ultrasonic wave. By applying the colorant (B) together with an organic solvent to a high-pressure jet nozzle type disperser or an ultrasonic disperser,
According to the above principle, the colorant (B) is finely dispersed in the organic solvent.

Specific examples of the high-pressure injection nozzle type disperser include a microfluidizer (manufactured by Mizuho Industry Co., Ltd.), De
BEE2000 (manufactured by Japan BEE), Gorin-type homogenizers G15 and G1000, Ranier-type homogenizers R56, R118, R2000 (manufactured by APV Homogenizer), Nanomizer (manufactured by Nanomizer), Ultra Turrax T50 (manufactured by Ika Japan), and the like. No. Further, as a dispersing machine using ultrasonic dispersing, Sonorator (manufactured by Sonic Corporation), T.V. K. Micromizer (manufactured by Tokushu Kika Kogyo Co., Ltd.) and the like.

The solid content of the mixture of the colorant (B) and the organic solvent in the above dispersion step is usually 1 to 50% by weight, preferably 3 to 40% by weight, particularly preferably 5 to 30% by weight. When the solid content concentration is 50% by weight or more, the thixotropic properties after dispersion become too high, which makes handling difficult. In the case of repeated dispersion, there is a problem that a predetermined pressure is not applied due to foaming. If it is less than%, it is inappropriate from an economical point of view.

The pressure applied to the mixture of the colorant (B) and the organic solvent in the dispersion step is usually 10 to 255 MPa, preferably 50 to 2,000 MPa, particularly preferably 100 to 2,000 MPa.
1,000 MPa. When the pressure is less than 10 MPa,
Colorant (A) dispersion particle size is not small, 2,500MP
If it exceeds a, it is not preferable from the viewpoint of the durability of the device. The temperature of the mixture of the colorant (B) and the organic solvent in the dispersion step is usually from 0 to 100 ° C, preferably from 20 to 80 ° C, particularly preferably from 30 to 60 ° C. Since a large amount of collision energy is generated during the treatment, a large cooling device is required to keep the treatment temperature below 0 ° C., which is economically disadvantageous. When the treatment temperature exceeds 60 ° C., reaggregation of the pigment and the like are apt to occur, which is not preferable. Depending on the type of the colorant (B), the dispersion may not reach the target level in a single treatment. In this case, the treatment is preferably repeated through a disperser. The number of treatments is usually 1 to 50
Times, preferably 1 to 30 times, particularly preferably 1 to 10 times.

The dispersion particle size d50 of the colorant (B) treated by the high-pressure jet nozzle type disperser is usually 20 μm or less, preferably 10 μm or less, particularly preferably 0.01 to 3 μm.
It is. When the dispersion particle diameter d50 of the colorant (B) exceeds 20 μm, the color sharpness at the time of forming a coating film is poor.

When the colorant (B) is dispersed in an organic solvent, it is preferable to use a pigment dispersant for the purpose of improving the dispersibility of the colorant (B). Examples of the pigment dispersant include a pigment dispersant containing a functional group having adsorptivity to the pigment. Examples of the functional group having adsorptivity to the pigment include acidic groups such as a phosphoric acid group, a carboxylic acid group, a sulfonic acid group, and a sulfamic acid group and neutralizing bases thereof, amino groups and neutralizing bases of amino groups, and quaternary. Ammonium base,
Examples include an amide group and an imide group. Examples of the main skeleton of the pigment dispersant include (co) polymers of vinyl monomers such as acrylates, styrene, and vinyl acetate, and polyethers, polyesters, polycaprolactones, polyamide polyamines, and copolymers thereof.

The pigment dispersant may be a low molecular weight compound or a high molecular weight compound. From the viewpoint of dispersion stability and compatibility with the resin (A), the pigment dispersant preferably has a weight average molecular weight of 1000 by gel permeation chromatography (GPC). ~ 500,
000, particularly preferably 1500 to 300,000. The pigment dispersant preferably has good compatibility with the resin (A) in order to stably disperse the pigment in the matrix. The SP value of the pigment dispersant and the SP value of the resin (A)
The difference from the value (ΔSP) is usually 0 from the viewpoint of compatibility between the two.
~ 1.0, preferably 0 ~ 0.8, particularly preferably 0 ~ 0
0.5.

Examples of the pigment dispersant include “Dispe”
rbyk-170 "," Disperbyk-111 "
(Big Chemie Japan Co., Ltd.), "Texahole" (San Nopco Co., Ltd.), "Dispalon DA-7"
05 "(manufactured by Kusumoto Kasei Co., Ltd.)," Ajispar PN41
1 ".

In the present invention, the dispersion of the colorant (B) and the organic solvent treated by the high-pressure jet nozzle disperser is added to the reactive group-containing prepolymer (A-
1) Dissolve or disperse the elongating agent and / or the crosslinking agent (A-2) and other resin (C) if necessary.
As the content of the colorant (B) in the dispersion of the prepolymer (A-1) and the dispersion of the colorant (B) and the organic solvent treated by the disperser, the content of the resin (A) And usually 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the other resin (C) used as required.
Parts by weight, particularly preferably 2 to 20 parts by weight. The above-mentioned dissolved dispersion is dissolved or dispersed in an organic solvent so as to have a solid concentration of 20 to 95% by weight, preferably 25 to 90% by weight before emulsification or dispersion in an aqueous medium. The organic solvent used is the same as in the above (D).

When emulsifying or dispersing the above-mentioned dissolved dispersion in an aqueous medium, the prepolymer (A-1) is subjected to an elongation and / or cross-linking reaction with an elongation agent and / or a cross-linking agent (A-2), The coloring is performed while the resin (A) is being formed, and the granulation is performed to obtain the colored resin particles of the present invention. On this occasion,
The elongating agent and / or the cross-linking agent (A-2) may be preliminarily mixed in the above-mentioned dissolved dispersion, or may be dissolved or dispersed in an aqueous medium. This method is capable of lowering the viscosity of the dissolution or dispersion, is advantageous for reducing the particle size of the particles during emulsification and dispersion, sharpening the particle size distribution, a polymer resin that is hardly soluble in an organic solvent, It has the feature that the crosslinked resin can be made into particles.

As the aqueous medium, water alone may be used, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohols (eg, methanol, isopropanol, ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolves (eg, methylcellosolve), and lower ketones (eg, acetone, methylethylketone). The amount of the solvent used is water 1
The amount is usually 0 to 50 parts by weight, preferably 0 to 30 parts by weight with respect to 00 parts by weight.

The amount of the aqueous medium used is usually 50 to 2,000 parts by weight, preferably 70 to 800 parts by weight, based on 100 parts by weight of the solution or dispersion.

As the emulsifier or dispersant to be used, known surfactants, aqueous polymers and the like can be used. The amount of the emulsifier or dispersant to be used is generally 0.1 to 10 parts of the above-mentioned solution or dispersion.

Examples of the surfactant include anionic surfactants such as carboxylic acid or a salt thereof, a sulfate ester salt, a salt of a carboxymethylated product, a sulfonate salt and a phosphate ester salt; quaternary ammonium salt type, amine salt Cationic surfactants such as types; carboxylate type amphoteric surfactants (amino acid type amphoteric surfactants, betaine type amphoteric surfactants, etc.), sulfate ester type amphoteric surfactants, sulfonate type amphoteric surfactants Surfactants, amphoteric surfactants such as phosphate ester type amphoteric surfactants; and nonionic surfactants such as alkylene oxide addition type and polyhydric alcohol type.

Examples of the aqueous polymer include cellulosic compounds such as carboxymethylcellulose, hydroxypropylcellulose and saponified products thereof; polyvinyl alcohol, starch, gum arabic; polyalkylene compounds such as polyethylene oxide, polypropylene oxide and polytetramethylene oxide. A side or the like is used.

In order to sharpen the particle size distribution of the emulsified or dispersed product, it is preferable to carry out the emulsifying or dispersing process in the presence of organic or inorganic fine particles. The organic or inorganic fine particles are emulsified or dispersed by previously dispersing them in an aqueous dispersion medium. Organic fine particles include copolymers of vinyl monomers such as styrene, (meth) acrylic acid and (meth) acrylate, and inorganic fine particles include calcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide, and aluminum hydroxide. Is mentioned.

The size of the fine particles is usually from 0.01 to 100.
μm, and may be appropriately selected depending on the intended use of the resin fine particle composition. The use amount of the fine particles is usually 1 to 100 parts by weight based on 100 parts by weight of the above-mentioned dissolved or dispersed liquid. The temperature at the time of emulsification or dispersion is usually 0 to 150
° C, preferably 20-98 ° C. It may be at normal pressure or under pressure.

The apparatus for emulsifying or dispersing is not particularly limited as long as it is generally commercially available as an emulsifier or disperser. For example, a homogenizer (manufactured by IKA),
Batch type emulsifiers such as Polytron (Kinematica), TK Auto Homo Mixer (Tokusai Kika), Ebara Milder (Arihara Seisakusho), TK Pipeline Homo Mixer (Toki Kika), Continuous emulsifiers such as colloid mills (manufactured by Shinko Pantech), slashers, trigonal wet pulverizers (manufactured by Mitsui Miike Kakoki Co., Ltd.), Capitrons (manufactured by Eurotec), fine flow mills (manufactured by Taiheiyo Kiko Co., Ltd.), High-pressure emulsifier such as microfluidizer (manufactured by Mizuho Industries), Nanomizer (manufactured by Nanomizer), APV Gaurin (manufactured by Gaurin), membrane emulsifier such as membrane emulsifier (manufactured by Kyoika Kogyo), vibro mixer (cooled) And vibrating emulsifiers such as an ultrasonic homogenizer (manufactured by Branson) and the like.

The obtained emulsion or dispersion is desolvated to obtain colored resin particles. The size of the colored resin particles (D
50) is usually 0.1 to 500 μm, and the particle size distribution (volume average particle size Dv / number average particle size Dn) is usually 1.05 to
5.0, which may be set as appropriate according to the application to be used.

In the present invention, when forming the resin fine particle composition, other known additives may be used depending on the application. Examples of the additives include a filler, an antistatic agent, a dye, a release agent, a charge control agent, an ultraviolet absorber, and an antioxidant.

Examples of the filler include titanium oxide and talc. Examples of the antistatic agent include a neutralized product of polystyrene sulfonic acid, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. As the dye, Sudan Black S
M, First Yellow G, Rhodamine FB, Rhodamine B Lake, Oil Yellow GG, Orazole Brown B and the like. Examples of the release agent include polyolefin wax (polyethylene wax, polypropylene wax, etc.), long-chain hydrocarbon (paraffin wax, sasol wax, etc.), carbonyl group-containing wax (carnauba wax, montan wax, trimethylolpropane tribehenate, Tristearyl trimellitate,
Ethylenediaminedibehenylamide, distearylketone, etc.). Examples of the charge control agent include nigrosine dyes, quaternary ammonium base-containing compounds, quaternary ammonium base-containing polymers, metal-containing azo dyes, salicylic acid metal salts, substituted salicylic acid metal salts, sulfonic acid group-containing polymers, and phosphoric acid group-containing polymers. No. Examples of the ultraviolet absorber include hindered amine and hindered phenol. As an antioxidant, BH
T and the like.

The colored resin particles and the above-mentioned other additives may be mixed at the time of forming a dispersion in an aqueous medium. More preferably, the mixture is added and dispersed.
In the present invention, the additive does not necessarily need to be mixed when forming particles in an aqueous medium,
After the particles are formed, they may be added. For example, after forming particles containing no dye, a dye may be added by a known dyeing method.

The colored resin particles of the present invention can be obtained by solid-liquid separation using a centrifuge, a spacra filter, a filter press or the like, and drying the obtained powder.
As a method for drying the obtained powder, a known apparatus such as a fluidized-bed dryer, a reduced-pressure dryer, a circulating dryer, and an airflow dryer can be used. If necessary, the particles can be classified using a wind classifier or the like to obtain a predetermined particle size distribution.

[0076]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the following description, "parts" indicates parts by weight and "%" indicates% by weight.

Production Example 1 [Synthesis of High Molecular Weight Polyester (A-1)] 542 parts of bisphenol A ethylene oxide 2 mol adduct, 192 parts of bisphenol A propylene oxide 2 mol adduct 192
Parts, 300 parts of isophthalic acid and 49 parts of terephthalic acid are polycondensed at 230 ° C. for 6 hours under normal pressure, and then 10 to 15 mm
The mixture was reacted for 5 hours while being dehydrated under reduced pressure of Hg to obtain a high molecular weight polyester having a number average molecular weight of 7,300 and a weight average molecular weight of 28,000.

Production Example 2 [Synthesis of low molecular weight polyester (A-2)] 378 parts of bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 2 mol adduct 402
Parts, 100 parts of isophthalic acid, 205 parts of terephthalic acid and 2 parts of dibutyltin oxide.
C. for 6 hours and then react for 5 hours while dehydrating at a reduced pressure of 10 to 15 mmHg to obtain a number average molecular weight of 280.
0, a low molecular weight polyester having a weight average molecular weight of 5100 was obtained.

Production Example 3 [Synthesis of Isocyanate Group-Containing Prepolymer (A-1-1)] In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 358 parts of a 2 mol adduct of bisphenol A ethylene oxide, Bisphenol A propylene oxide 2
381 parts of the molar adduct, 200 parts of isophthalic acid, 127 parts of terephthalic acid and 2 parts of dibutyltin oxide were added, and reacted at 230 ° C. for 8 hours under normal pressure.
After reacting for 5 hours while dehydrating under reduced pressure of mmHg, 80
C., and reacted with 110 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain a weight average molecular weight of 12
000, an isocyanate group-containing prepolymer (A-1-1) having an NCO content of 1.02% in ethyl acetate (solid content: 75%) was obtained.

Production Example 4 [Ketimine compound (blocked product of amine: A-1-
2) Synthesis] 30 parts of isophoronediamine and 70 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stir bar and a thermometer, and reacted at 50 ° C. for 5 hours to obtain a ketimine compound.

Example 1 [Synthesis of Colored Resin Particles (1)] Cyanine Blue KRO
20 parts (manufactured by Sanyo Pigment Co., Ltd.), 67 parts of ethyl acetate, and 13 parts of a pigment dispersant (Disper Byk-170: manufactured by BYK Japan) are mixed and dispersed by a high-pressure injection nozzle type dispersing machine [Gaulin-type homogenizer 15M-8TB]. went. The pressure at the time of dispersion is 51 MPa, and the processing speed is 1,000.
ml / min, the number of passes was 1, the temperature of the mixture at the time of introduction into the dispersing machine was 16 ° C., the temperature of the discharged dispersion was 55 ° C., and the particle size d50 of the pigment was 0.39 μm. Dispersion 2 above
While stirring 5 parts at room temperature, a high molecular weight polyester (A
-1) A solution prepared by dissolving 30 parts of 65 parts of low molecular weight polyester (A-2) in 36 parts of ethyl acetate and a dispersion of 5 parts of carnauba wax dispersed in 45 parts of ethyl acetate are added over 30 minutes and solidified. A mixed dispersion (1) of a resin and a colorant having a concentration of 50% was obtained. 200 ion-exchanged water in a beaker
, 35 parts of a 10% suspension of hydroxyapatite (Supatite 10 manufactured by Nippon Chemical Industry Co., Ltd.) and 0.1 part of sodium dodecylbenzenesulfonate were added and uniformly dissolved.
Then, the temperature was adjusted to 20 ° C, and the temperature was adjusted to 5000 with a TK homomixer.
While stirring at rpm, 100 parts of the mixed dispersion of the above resin and colorant was added and stirred for 10 minutes. Then, the mixture was transferred to a kolben equipped with a stirring rod and a thermometer, the temperature was raised to 50 ° C., the solvent was removed under reduced pressure, and the cake was separated by filtration.
The dispersion was washed in 450 parts of hydrochloric acid and filtered again. This operation was further performed once with 200 parts of 5% hydrochloric acid and 1% sodium hydroxide 2
After repeating once with 00 parts and three times with 250 parts of ion-exchanged water, drying with a normal air dryer and air classification were performed to obtain a particle diameter d50 of 20.
μm [colored resin particles (1)] were obtained. In addition, 50 parts of ethyl acetate dispersion liquid of carnauba wax was used, in which 50 parts of zirconia beads (particle size: 0.8) were charged and dispersed for 2 hours with a Glen Mill (manufactured by Asada Iron Works).

Example 2 [Synthesis of Colored Resin Particles (2)] Permanent Red 4R
20 parts, ethyl acetate 74 parts, pigment dispersant (Disper
byk-111: manufactured by BYK Japan KK) and mixed with a high pressure jet nozzle type dispersing machine [Gaulin type homogenizer 15M-8TA]. The pressure at the time of dispersion was 51 MPa, the processing speed was 1,000 ml / min, the number of passes was three, the temperature of the mixture at the time of inputting the disperser was 20 ° C., and the temperature of the discharged dispersion was 52 to 61 ° C. Was. The dispersion was cooled to 20 ° C. with ice water for each pass, and then processed by a disperser. The particle size d50 of the pigment was 0.41 μm. The isocyanate group-containing prepolymer (A-1) described in Production Example 3 was stirred while stirring 25 parts of the above dispersion at room temperature.
133 parts of an ethyl acetate solution of 52-1 and 52 parts of ethyl acetate were continuously charged over 30 minutes to obtain a mixed dispersion (2) of a resin and a colorant having a solid content of 50%. The same operation as in Example 1 was performed except that the mixed dispersion of the resin and the colorant was used, to thereby obtain [Colored resin particles (2)] having a particle size d50 of 20 μm. In this case, water becomes the elongating agent.

Example 3 Synthesis of Colored Resin Particles (3) Benzidine Yellow 10
Parts, 85 parts of ethyl acetate, and 5 parts of a pigment dispersant (Texahole: manufactured by San Nopco Co., Ltd.) were mixed and dispersed using a high-pressure injection nozzle type disperser [Gaulin-type homogenizer 15M-8TA]. The pressure at the time of dispersion was 51 MPa, the processing speed was 1,000 ml / min, the number of passes was five, the temperature of the mixed solution at the time of putting the disperser was 20 ° C., and the temperature of the discharged dispersion was 55 to 63 ° C. Was. 20 dispersions with ice water per pass
After cooling to ° C., the mixture was processed by a disperser. The particle size d50 of the pigment was 0.28 μm. The dispersion 70
While stirring at room temperature, 90 parts of the low molecular weight polyester (A-2) described in Production Example 2, 13 parts of an ethyl acetate solution of the isocyanate group-containing prepolymer (A-1-1) described in Production Example 3, and ethyl acetate 47 parts were added and dissolved over 30 minutes, and 0.15 part of a ketimine compound was further mixed to obtain a mixed dispersion liquid (3) of a resin and a colorant having a solid concentration of 50%. Except for using this mixed dispersion, the same operation as in Example 1 was performed to obtain [Colored Resin Particles (3)] having a particle size d50 of 20 μm.

Comparative Example 1 [Synthesis of Colored Resin Particles (4)] 95 parts of the low-molecular polyester described in Production Example 1, 5 parts of cyanine blue KRO (manufactured by Sanyo Dye), a pigment dispersant (Disper Byk-11)
1: BIC Chemie Japan) 2 parts, Carnauba wax 5 parts Henschel mixer (Mitsui Miike Kakoki Co., Ltd. FM)
10B), and kneaded with a twin-screw kneader (PCM-30, manufactured by Ikegai Co., Ltd.). Then, supersonic jet crusher LabJet (Nippon Pneumatic Industries, Ltd.)
And then stirred at 35 ° C. for 3 hours to obtain a mixed dispersion (4) of a resin and a colorant having a solid content of 50%. Except for using this mixed dispersion, the same operation as in Example 1 was performed, and the particle size d was obtained.
Comparative [colored resin particles (4)] having a particle diameter of 50 μm and 20 μm was obtained.

Comparative Example 2 [Synthesis of Colored Resin Particles (5)] The pigment described in Comparative Example 2 was 5 parts of permanent red 4R, and the pigment dispersant was Disper.
(Byk-111: manufactured by Big Chemie Japan) except that the amount was changed to 2 parts.
Thus, m colored resin particles (5) were obtained.

Comparative Example 3 [Synthesis of Colored Resin Particles (6)] All except that the pigment described in Comparative Example 2 was changed to 7 parts of benzidine yellow and the pigment dispersant was changed to 2.1 parts of Texahole (manufactured by San Nopco). The same operation as in Comparative Example 1 was performed to obtain [Mixed dispersion of resin and colorant (6)] and [Colored resin particles (6)] having a particle size d50 of 20 μm.

Physical property measurement example 1 The pigment particle size (particle size d) of [Pigment dispersion liquid (1)] to [Pigment dispersion liquid (6)] obtained in Examples 1 to 3 and Comparative examples 1 to 3
50) and the content of pigment aggregates (particle size of 1 μm or more) were measured with a laser diffraction type particle size distribution analyzer “LA-920” (manufactured by Horiba, Ltd.). Table 1 shows the evaluation results. The smaller the pigment particle size and the smaller the aggregate content, the better the pigment dispersibility.

Performance Evaluation Example 2 Cut samples of the [colored resin particles (1)] to [colored resin particles (6)] obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were prepared, and were measured with a transmission electron microscope ( (TEM) “H7100” (manufactured by Hitachi, Ltd.) was used to observe the pigment dispersion state on the cross section of the colored resin particles. (Magnification 10,000 times) The dispersion state of the pigment was determined according to the following evaluation criteria. Table 3 shows the results. A: No pigment aggregate (0.5 μm or more). ：: 1 to 3 pigment aggregates (0.5 μm or more). Δ: There are 3 to 9 pigment aggregates (0.5 μm or more). ×: There are 10 or more pigment aggregates (0.5 μm or more). Performance Evaluation Example 3 0.1 g of the [colored resin particles (1)] to [colored resin particles (6)] obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was 5 cm in length.
× A glass piece of 5 cm in width was placed on the glass piece, and another glass piece was placed from above while heating on a hot plate, followed by applying pressure to form a resin film. The color difference and haze degree of this resin film were measured with a color difference meter “NDH-300A” (manufactured by Nippon Denshoku Industries Co., Ltd.). Table 2 shows the evaluation results. The color difference (a *, b *)
The larger the absolute value of each measured value, the more vivid the color, and the smaller the measured value, the more transparent the haze.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

The method of the present invention has the following effects. 1. The pigment dispersion is very finely dispersed, and the dispersion stability is excellent over time. 2. The pigment dispersibility in the resin particles is good and the resulting coating film has excellent color sharpness and transparency. Due to the above effects, the colored resin particles obtained from the method of the present invention are powder coating, resin for hot-melt molding, spacers for manufacturing electronic components such as liquid crystals, standard particles for electronic measurement equipment, electrophotography, It is extremely useful as a resin particle useful for a toner used for electrostatic recording, electrostatic printing, etc., various hot melt adhesives, and other molding materials.

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[Procedure amendment]

[Submission date] April 24, 2002 (2002.4.2
4)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction contents]

The solid content of the mixture of the colorant (B) and the organic solvent in the above dispersion step is usually 1 to 50% by weight, preferably 3 to 40% by weight, particularly preferably 5 to 30% by weight. If the solid concentration exceeds 50% by weight, the thixotropic properties after dispersion become too high, which makes handling difficult. In the case of repeated dispersion, there is a problem that a predetermined pressure is not applied due to foaming. If the amount is less than% by weight, it is not economically appropriate.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0089

[Correction method] Change

[Correction contents]

[0089]

[Table 1]

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4F070 AA46 AA47 AA53 AC74 AC87 AC88 AC89 AE04 AE08 AE28 CA02 CA03 CB03 CB12 CB13 DA33 DC13 DC14 FA04 FA05 FA17 FB01 FB06 FC09 4J002 AA002 CD001 CD002 CF001 CF002 CK021 CK012 CK012 CK012 CK012 CK012 CK012 CK012 CK012 CK012 CK012 CK012 CK012 CK012

Claims (7)

[Claims] 1. A colorant (B) and an organic solvent (D) are mixed so as to have a solid content concentration of 1 to 50% by weight, and the mixture is colored using a high-pressure jet nozzle disperser or an ultrasonic disperser. The agent is dispersed in an organic solvent, and the reactive group-containing prepolymer (A-1) which is a precursor of the resin (A) is dissolved or dispersed in the dispersion so that the solid content concentration becomes 20 to 95% by weight. Then, the dissolved or dispersed liquid is emulsified or dispersed in an aqueous medium, and (A-1) is elongated and / or cross-linked by an elongating agent and / or a cross-linking agent (A-2) to form the resin (A). A method for producing colored resin particles, comprising forming and granulating. 2. The reactive group of the prepolymer (A-1) is a reactive group selected from the group consisting of an isocyanate group, a blocked isocyanate group and an epoxy group, and (A-2) is The production method according to claim 1, which is a compound (A-2-1) having or generating active hydrogen. 3. The method according to claim 2, wherein (A-2-1) is water or a ketimine compound. 4. The method according to claim 1, wherein the resin (A) is a resin selected from the group consisting of a polyester resin, a polyurethane resin, a polyurea resin and an epoxy resin. 5. The pigment according to claim 1, wherein the colorant (B) is a white pigment, a yellow pigment, an orange pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment or a black pigment. Colored resin particles. 6. The reactive group-containing prepolymer (A-
1), using another resin (C) together with an elongating agent and / or a crosslinking agent (A-2), wherein the weight ratio of the (A-1) to the (C) is 2:98 to 100: 0. The production method according to claim 1, which is in a range. 7. The method according to claim 1, wherein the resin (C) is a resin selected from the group consisting of a vinyl resin, a polyester resin, a polyurethane resin, a polyurea resin and an epoxy resin.