JP2002212304A - Colored resin particle and method for producing thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain colored resin particles good in dispersing characteristics of pigments and capable of forming a paint film excellent in color sharpness and transparency. SOLUTION: Colored resin particles are obtained by dispersing a colorant (C) in a resin (B) with a dispersant (A) having a functional group selected from a phosphoric acid (phosphate) group, a sulfonic acid (sulfonate) group and a sulfuric acid (sulfate) group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to colored resin particles which form a coating film having a good pigment dispersibility and excellent color sharpness and transparency. More specifically, powder coatings with excellent heat-melt properties and powder flowability, resins for hot-melt molding, spacers for the production of electronic components such as liquid crystals, standard particles for electronic measurement equipment, electrophotography, electrostatic recording, static The present invention relates to a colored resin particle useful for a toner used in electroprinting 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. The above-described method for producing resin particles by emulsification / dispersion is not suitable for forming particles of a polymer resin or a cross-linkable resin that is hardly soluble in an organic solvent. A solvent solution is prepared and emulsified / dispersed with a polyfunctional extender capable of reacting with the prepolymer.
By forming a crosslinked resin, resin properties such as rheology required for the above applications can be designed in a wide range.
However, when a pigment or the like is dispersed to color particles to be designed as a toner used for powder coating, electrophotography, electrostatic recording, electrostatic printing, etc., adjustment of an organic solvent solution / dispersion, emulsification / dispersion In addition, secondary aggregation of the pigment may occur in each step of solvent removal, and there is a problem that the sharpness of color and transparency of the coating film are deteriorated. In order to solve such a problem, improvement in pigment dispersibility by a pigment dispersant has been proposed. Japanese Patent Application Laid-Open No. H11-72958 discloses, as an application example of a toner, an acid value of 11 mgKOH / g to 27 mg.
The utility of a polymer dispersant having KOH / g or less and an amine value of 1 to 100 is disclosed. However, although this dispersant retains pigment dispersibility at a temperature of about 30 ° C., the pigment dispersing stability at a high temperature of, for example, about 50 ° C. is inferior and a long time is required for the solvent removal step. Have a point. Further, there is also a problem that the dispersibility of the pigment is deteriorated when an elongating agent is added, so that the in-water elongation method cannot be taken, and a wide range of resin designs cannot be designed.

[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 made intensive studies to solve the above-mentioned problems, and as a result, have obtained a colored resin particle having good pigment dispersibility and excellent color sharpness and transparency of a coating film. Found that it was effective to disperse the pigment with a dispersant having a specific functional group, and reached the present invention. That is, the present invention provides a dispersant (A) in which the colorant (C) in the resin (B) has a functional group selected from the group consisting of a phosphoric acid (salt) group, a sulfonic acid (salt) group, and a sulfuric acid (salt) group. Resin (C) dispersed by a dispersant (A) having a functional group selected from the group consisting of a phosphoric acid (salt) group, a sulfonic acid (salt) group, and a sulfuric acid (salt) group. Dissolving or dispersing the resulting resin (B) in an organic solvent, emulsifying or dispersing the dissolved or dispersed liquid in an aqueous medium, and granulating; and Precursor of resin (B) in which colorant (C) is dispersed by dispersant (A) having a functional group selected from the group consisting of phosphoric acid (salt) group, sulfonic acid (salt) group and sulfuric acid (salt) group The reactive group-containing prepolymer (α) is dissolved or dispersed in an organic solvent, Or emulsifying or dispersing the dispersion in an aqueous medium containing an elongating agent and / or a crosslinking agent (β), and elongating and / or cross-linking (α) to form a resin (B) and granulation. This is a method for producing colored resin particles.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, the dispersant (A) having a functional group selected from the group consisting of a phosphoric acid (salt) group, a sulfonic acid (salt) group, and a sulfuric acid (salt) group
May be a low molecular weight compound or a high molecular weight compound, but preferably has a weight average molecular weight of 1000 to 500,000 by gel filtration chromatography (GPC) from the viewpoint of dispersion stability and compatibility with the resin (B). Preferably it is 1500-300,000. The phosphoric acid (salt) group, sulfonic acid (salt) group and sulfuric acid (salt) group function as adsorption sites for the pigment. Phosphoric acid (salt) groups include those partially converted into alkyl (C1-20) esters.
Salts include alkali metal salts (such as lithium salts, sodium salts, and potassium salts), alkaline earth metal salts (such as magnesium and calcium salts), and amine salts (such as trimethylamine, triethylamine, triethanolamine, dimethyloctylamine, and dimethyllauryl). Amines, dimethylaminoethanol, aminomethylpropanol, pyridine, ethylenediamine, etc.), ammonium salts and the like. When the dispersant (A) is a polymer compound (including an oligomer), its main skeleton is a (co) polymer of a vinyl monomer, a polyether, a polyester, a polyester, a polycaprolactone, and a copolymer of these. Those selected from the group are preferred. The content (molecular weight g / equivalent) of a phosphoric acid (salt) group, a sulfonic acid (salt) group or a sulfuric acid (salt) group in the dispersant (A) is usually from 200 to 2,000.
0, preferably 400-5000.

The dispersant (A) is, for example, copolymerized with a vinyl monomer having a phosphoric acid (salt) group or a sulfonic acid (salt) group and another vinyl monomer; Directly esterifying or esterifying a compound having a hydrogen group with a compound having a phosphoric acid (ester) group, a sulfonic acid (ester) group, or a sulfuric acid (ester) group, or one or more active hydrogens at the terminal Reacting a compound having a group with a sulfating agent and a sulfonating agent to introduce a sulfonic acid group and a sulfate group; sulfonating a compound having a phenyl group with a sulfonating agent; double bonds in the molecule And a method of reacting a compound having the above formula with sodium acid sulfite.

The vinyl monomers having a sulfonic acid (salt) group described above include methyl vinyl sulfonate, styrene sulfonic acid (salt), α-methylstyrene sulfonic acid (salt), sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid (salt), 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid (salt), 2- (meth) acryloyloxyethanesulfonic acid (salt) ), 3-
(Meth) acryloyloxy-2-hydroxypropanesulfonic acid (salt), 2- (meth) acrylamide-2-
Methylpropanesulfonic acid (salt), 3- (meth) acrylamide-2-hydroxypropanesulfonic acid (salt),
Alkyl (C3-18) allyl sulfosuccinic acid (salt) and the like. Vinyl monomers having a phosphoric acid (salt) group include hydroxyalkyl (meth) acrylate monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate and phenyl-2.
-Acryloyloxyethyl phosphate, alkylphosphonic acid (meth) acrylates, for example, 2-acryloyloxyethylphosphonic acid (salt) and the like. Other vinyl monomers include the following (1) to (6). (1) Aromatic vinyl hydrocarbon: styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, etc. (2) Carboxyl group-containing vinyl monomer and its Salts: (meth) acrylic acid, (anhydride) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, etc. (3) Hydroxyl group-containing vinyl monomer Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxyethylpropenyl ether, (4) Amino group-containing vinyl monomers include aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth).
Acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetate Amino acrylate, vinyl imidazole,
N-vinylpyrrole, N-vinylthiopyrrolidone, N-
Arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole,
And aminoimidazole. Of these, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
N-aminoethyl (meth) acrylamide, morpholinoethyl (meth) acrylate, and 2-vinylpyridine. (5) Epoxy group-containing vinyl monomer such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc. (6) alkyl (meth) acrylate alkyl having an alkyl group having 1 to 20 carbon atoms ( Meta)
Acrylates, for example methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, eicosyl (meth) acrylate, and the like.

In the above, the polymerization can be carried out by a known polymerization method such as suspension, emulsification, solution polymerization or the like using the above-mentioned monomers using a radical polymerization catalyst. The content of the other vinyl monomer as a structural unit is usually 0 to 98 mol%, preferably 5 to 95 mol%. The polymerization temperature is
The reaction time is usually 10 to 200 ° C, preferably 40 to 180 ° C, and the reaction time is usually 1 to 48 hours, preferably 4 to 2 hours.
4 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.

In the above, as the compound having one or more active hydrogen groups at the terminal, 1 to 3 having 6 to 32 carbon atoms may be used.
Examples thereof include a hydric alcohol, a polyether, an aliphatic polyester, an aromatic polyester, and polycaprolactone. As a C1-C32 trihydric alcohol,
Hexanol, octanol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol,
Benzyl alcohol, 1,6-hexanediol, 1,
8-octanediol and the like. Examples of the polyether include polyalkylene ether glycols having a weight average molecular weight of 100 to 10,000 (polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols having 5 to 18 carbon atoms (1,4-cyclohexane di C2-C18 alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, α- Olefin oxide) adducts (addition mole number is 2 to 20).

Examples of the aliphatic polyester and aromatic 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, a diol (1) and a trivalent or higher polyol (2) are used. As a polycarboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof, a dicarboxylic acid (3) and a trivalent or higher polycarboxylic acid (4) are used. These acid anhydrides or lower alkyl esters are mentioned. The ratio of the polyol to the polycarboxylic acid is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1, more preferably 1.3
/ 1 to 1.02 / 1.

As the diol (1), alkylene glycols (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, hydrogen) Bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxides of the above alicyclic diols (ethylene Oxides, propylene oxide, butylene oxide, etc.) adducts; alkylene oxides of the above bisphenols (ethylene oxide,
Propylene oxide, butylene oxide, etc.) adducts and the like. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols, and alkylene glycols having 2 to 12 carbon atoms. Is a combination of Examples of the trihydric or higher polyol (2) include polyhydric aliphatic alcohols having 3 to 8 or more valences (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. Among these, preferred are polyhydric aliphatic alcohols having 3 to 8 or more valences and alkylene oxide adducts of novolak resins, and particularly preferred are alkylene oxide adducts of novolak resins.

The dicarboxylic acids (3) include alkylenedicarboxylic acids (succinic acid, adipic acid, sebacic acid, dodecenylsuccinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, etc.); alkenenedicarboxylic acids (maleic acid, A branched alkylenedicarboxylic acid having 8 or more carbon atoms [dimer acid, alkenyl succinic acid (dodecenyl succinic acid,
Pentadecenyl succinic acid, octadecenyl succinic acid, etc.), alkyl succinic acids (decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid) Etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (4) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid,
Pyromellitic acid). In addition, as the dicarboxylic acid (3) or the trivalent or higher polycarboxylic acid (4), the above-mentioned acid anhydride or lower alkyl ester (eg, methyl ester, ethyl ester, isopropyl ester) may be used.

Examples of polycaprolactone include polyadducts of γ-butyrolactone and ε-caprolactone having a weight average molecular weight of 100 to 5,000.

Examples of the compound having a phosphoric acid (ester) group, a sulfonic acid (ester) group, and a sulfuric acid (ester) group include phosphoric acid, (mono, di, tri) alkyl esters having 1 to 12 carbon atoms, sulfuric acid, and chlorinated acid. Sulfonic acid, sulfuric anhydride, fuming sulfuric acid, sulfamic acid and the like can be mentioned. Sulfating agent,
Examples of the sulfonating agent include sulfuric acid, chlorosulfonic acid, sulfuric anhydride, fuming sulfuric acid, and sulfamic acid. In the above, the reaction can be synthesized by esterification, sulfonation, and sulfation of the compound by a known method. The reaction temperature is usually 0 to 150 ° C, preferably 10
To 100 ° C, and the reaction time is usually 1 to 48 hours, preferably 4 to 24 hours.

In the above description, examples of the compound having a phenyl group include polystyrene. Examples of the sulfonating agent include the same ones as described above. The reaction temperature is generally 0 to 150 ° C, preferably 30 to
120 ° C.

The dispersant (A) preferably has good compatibility with the resin (B) in order to stably disperse the pigment in the matrix. The SP value of the (A) and the dispersant (A) The difference from the SP value (ΔSP) is usually 0 to 1.0, preferably 0 to 0.8, and particularly preferably 0 to 0.5 from the viewpoint of compatibility between the two.

The amount of the dispersant (A) to be used is usually 1 to 100 parts by weight of the pigment, from the viewpoint of improving the dispersibility of the pigment and affecting various properties (such as chargeability and fluidity) due to moisture absorption.
The amount is 150 parts by weight, preferably 3 to 120 parts by weight, particularly preferably 5 to 100 parts by weight.
It is 0.5 to 80 parts by weight, particularly preferably 0.1 to 70 parts by weight.

In the present invention, any resin can be used as the resin (B) as long as it is a known resin. (Meth) alkyl acrylate copolymer, styrene-butadiene copolymer, acrylic acid-alkyl acrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Maleic anhydride copolymer; polyester resin, unsaturated polyester resin, polyamide resin, polyimide resin, polycarbonate resin, silicon resin as polycondensation resin; polyurethane resin, polyurea resin, epoxy resin as polyaddition resin; addition Examples of the polymer resin include a phenol resin, a melamine resin, and an aniline resin; examples of the other resin include an ionomer resin. Of these, preferred are vinyl resins, polyester resins,
Polyurethane resin, polyurea resin and epoxy resin.

The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. Examples of the vinyl monomer include the same ones as described above. 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 200 ° C, preferably 40 to 180 ° C, and the reaction time is usually 1 to 48 hours, preferably 4 to 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 a polycondensate of the polyol and the polycarboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof. Examples of the polyol include those similar to the diol (1) and the polyol (2) having a valency of 3 or more. Examples of the polycarboxylic acid or its anhydride or the lower alkyl ester thereof include the dicarboxylic acid (3) and the valency of 3 or more. And the same as the above-mentioned polycarboxylic acids (4) and their acid anhydrides or lower alkyl esters.

Examples of the polyurethane resin include a polyisocyanate (5), an active hydrogen group-containing compound (D), water, a polyol [the diol (1) and a polyol having a valency of 3 or more (2)], a dicarboxylic acid (3), and a dicarboxylic acid (3). Polycarboxylic acid (4), polyamine (6), polythiol (7)
And polyadducts with the like.

Examples of the polyisocyanate (5) 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 15 carbon atoms. 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, isocyanate) Nurate group, oxazolidone group-containing modified product, etc.) and a mixture of two or more thereof.
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.

Examples of the polyamine (6) include aliphatic polyamines (C2 to C18): aliphatic polyamine {C2
-C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) polyamine [diethylenetriamine,
Iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]; alkyl (C1 -C4) or hydroxyalkyl (C2 -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,
Tetrachlor-p-xylylenediamine, etc.), alicyclic polyamines (C4 -C15): 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,
Heterocyclic polyamines (C4 -C1) such as 4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline)
5): piperazine, N-aminoethylpiperazine, 1,
Aromatic polyamines (C6 to C20) such as 4-diaminoethylpiperazine and 1,4bis (2-amino-2-methylpropyl) piperazine: unsubstituted aromatic polyamines [1,2-, 1,3- and 1 2,4-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 i
Aromatic polyamines having a C1 -C4 alkyl group such as -propyl, butyl, etc., 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, and mixtures of these isomers in various proportions An aromatic polyamine 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-phenylene Diamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-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 polyamines having a secondary amino group [-NH2 of the above aromatic polyamines] Some or all of which are replaced by -NH-R '(R' is an alkyl group such as a lower alkyl group such as methyl and ethyl)] [4,4'-di (methylamino) diphenylmethane, 1-methyl- 2-methylamino-4-aminobenzene, etc.], polyamide polyamine: condensation of dicarboxylic acid (such as dimer acid) with excess (more than 2 moles per mole of acid) polyamines (such as the above-mentioned alkylenediamine, polyalkylene polyamine) Polyamines such as low molecular weight polyamide polyamines obtained by Len glycol etc.)
And hydrides of cyanoethylates.

Examples of the polyurea resin include a reaction product of the above-mentioned poly (di, tri) isocyanate (3) and amines (4).

Examples of the polythiol (7) include ethylenedithiol, 1,4-butanedithiol, and 1,6-hexanedithiol.

Examples of the epoxy resin include polyepoxide (8) and active hydrogen group-containing compound (D) water, polyol [the above diol (1) and tri- or higher polyol (2)], dicarboxylic acid (3), trivalent The above polycarboxylic acid (4), polyamine (6), polythiol (7)
And polyadducts of dicarboxylic acid (3) or tricarboxylic or higher polycarboxylic acid (4) with acid anhydride and the like.

The polyepoxide (8) of the present invention is not particularly limited as long as it has two or more epoxy groups in the molecule. Preferred as the polyepoxide (8) is a compound having 2 to 2 epoxy groups in the molecule from the viewpoint of the mechanical properties of the cured product.
It has six. The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide (8) is usually 65.
１０００1000, preferably 90-500.
If the epoxy equivalent exceeds 1,000, the crosslinked structure becomes loose and the cured product has poor physical properties such as water resistance, chemical resistance, and mechanical strength. is there.

Examples of the polyepoxide (8) 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 B 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. The polyepoxide of the present invention may be used in combination of two or more.

As the colorant (C) 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. Carbon black that has been subjected to a surface treatment can be used. Examples of the surface treatment method include polymer grafting, surface oxidation treatment, and surface adsorption treatment. 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, and may be appropriately selected.

The content of the colorant (C) is usually 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, particularly preferably 2 to 2 parts by weight, per 100 parts by weight of the resin (B).
0 parts by weight. Known dyes, magnetic powders and the like may be used in combination with the above pigments.

The colored resin particles of the present invention can be obtained by the following method. (I): The resin (B) in which the colorant (C) is dispersed by the dispersant (A) is dissolved or dispersed in an organic solvent, and the dissolved or dispersed liquid is emulsified or dispersed in an aqueous medium. , Granulate. (II): a reactive group-containing prepolymer (α), which is a precursor of the resin (B) in which the colorant (C) is dispersed by the dispersant (A), is dissolved or dispersed in an organic solvent, Emulsifying or dispersing the solution or dispersion in an aqueous medium containing an elongating agent and / or a crosslinking agent (β), and elongating and / or crosslinking (α) to form a resin (B);
Granulate.

In the above method (I), the colorant (C)
Can be dispersed in the resin (B) in the presence of the dispersant (A) without a solvent or, if necessary, using a solvent. As the solvent, toluene, xylene, ethyl acetate,
Methyl ethyl ketone or a mixed solvent of two or more thereof can be used. The amount of the solvent to be used is usually 0 to 300 parts, preferably 0 to 100 parts, more preferably 5 to 50 parts based on 100 parts of the total weight of the resin (B), the colorant (C) and the dispersant (A). . When a solvent is used, it is heated and removed under normal pressure or reduced pressure after the completion of emulsification and dispersion.

As a method for dispersing the colorant (C) in the dissolution / dispersion liquid, wet dispersion using a medium using zirconia beads or the like, or high shearing by a disper, a homomixer, a roll mill, a twin-screw kneader or the like is used. It can be carried out with a dispersed method. When emulsifying and dispersing the solution / dispersion of the resin (B), the colorant (C) and the dispersant (A), organic and inorganic fine particles are previously dispersed in an aqueous dispersion medium in order to sharpen the particle size distribution. After that, a method of emulsifying and dispersing the above-mentioned dissolved / dispersed liquid is preferable. Styrene,
Examples of inorganic fine particles such as copolymers of vinyl monomers such as (meth) acrylic acid and (meth) acrylic acid ester include calcium phosphate, hydroxyapatite, calcium carbonate, and titanium oxide. And aluminum hydroxide.

The size of the fine particles is usually 0.01 to 100.
μm, and may be appropriately selected depending on the intended use of the resin fine particle composition. The amount of the fine particles to be used is usually 1 to 100 parts of the dissolution / dispersion.

As the emulsifier or dispersant to be used in combination, 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 dissolution / dispersion liquid.

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, gelatin, starch, gum arabic, chitin,
Chitosan; polyalkylene oxides such as polyethylene oxide, polypropylene oxide and polytetramethylene oxide are used.

When the colored resin particles of the present invention are obtained by emulsifying and dispersing a dispersion of the resin (B), the colorant (C) and the dispersant (A), or a solvent solution of the dispersion in an aqueous medium. The dispersing device used for the above is not particularly limited as long as it is generally available as an emulsifier and a disperser. For example, a homogenizer (manufactured by IKA), a polytron (manufactured by Kinematica), a TK auto homomixer (special machine) Batch type emulsifiers such as Kaba Kogyo Co., Ltd., Ebara Milder (manufactured by Arihara Seisakusho), TK pipeline homomixer (manufactured by Tokushu Kika Kogyo), colloid mill (manufactured by Shinko Pantec),
Continuous emulsifier such as slasher, trigonal wet pulverizer (manufactured by Mitsui Miike Kakoki), Capitron (manufactured by Eurotech), fine flow mill (manufactured by Taiheiyo Kiko), microfluidizer (manufactured by Mizuho Industries), High pressure emulsifier such as Nanomizer (manufactured by Nanomizer), APV Gaurin (manufactured by Gaurin), membrane emulsifier such as membrane emulsifier (manufactured by Reika Kogyo), vibrating emulsifier such as vibro mixer (manufactured by Reika Kogyo) And an ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson).

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). As the temperature during dispersion,
Usually, 0 to 150 ° C (under pressure), preferably 40 to 98 ° C
It is. A higher temperature is preferred because the dispersion of the resin (B), the colorant (C) and the pigment dispersant (A), or the solvent solution of this dispersion has a low viscosity and is easy to disperse.

The amount of the aqueous medium used is usually 50 to 2,000 parts by weight, preferably 100 parts by weight, per 100 parts of the dissolution / dispersion of the resin (B), the colorant (C) and the dispersant (A).
１，1,000 parts by weight. Less than 50 parts by weight (α)
The state of dispersion becomes worse. If it exceeds 2,000 parts by weight, it is not economical.

The size of the obtained colored resin particles (D50)
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, all of which are appropriately set according to the intended use. I just need.

In the method (II), the reactive group-containing prepolymer (α) which is a precursor of the resin (B) is used in place of the resin (B) in the method (I), and the resin is emulsified or dispersed in an aqueous medium. When dispersing, the dispersing and / or crosslinking agent (β) in an aqueous medium is subjected to elongation and / or crosslinking reaction to form a resin (B), and granulation is performed. It is possible to lower the viscosity,
It is more preferable than the method (I) in that it is advantageous in reducing the particle size of the particles during dispersion and sharpening the particle size distribution, and enables the formation of particles of a polymer resin or a crosslinked resin that is hardly soluble in an organic solvent.

Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (α) and the extender and / or the crosslinking agent (β) include the following. : A combination of the reactive group contained in (α) is a functional group (α-1) capable of reacting with an active hydrogen compound, and (β) is a compound containing an active hydrogen group-containing compound (β-1). : A compound in which the reactive group of (α) is an active hydrogen group (α-2) and (β) is capable of reacting with an active hydrogen group (β-
2) Combination.

In the above, examples of the functional group (α-1) capable of reacting with the 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.

Examples of the active hydrogen group-containing compound (β-1) include polyamines, polyamines which may be blocked with a removable compound, polyols, polymercaptans and water. Of these, preferred are polyamines, polyamines which may be blocked with a removable compound, polyols and water. Examples of the polyamines include those similar to the above-mentioned polyamines (4).

The polyamines which may be blocked by a compound which can be eliminated include the polyamines (4)
And ketones having 3 to 8 carbon atoms (eg, acetone, methyl ethyl ketone, and methyl isobutyl ketone).

The polyols are preferably the same as the above-mentioned polyols (1), diols alone, or a mixture of a diol and a small amount of a trivalent or higher polyol. As polymercaptans, ethylenedithiol, 1,4
-Butanedithiol, 1,6-hexanedithiol and the like. Further, if necessary, a reaction terminator can be used together with (β-1). As a reaction terminator,
Monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.); monoamines blocked (ketimine compounds, etc.); monools (methanol, ethanol, isopropanol, butanol, phenol; monomercaptans (butylmercaptan, laurylmercaptan, etc.), etc. No.

The active hydrogen groups (α-2) of the prepolymer (α) in the above-mentioned include amino groups, hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), mercapto groups, carboxyl groups, and those which can be eliminated. An organic group blocked by a compound may, for example, be mentioned. Of these, preferred are an organic group in which an amino group, a hydroxyl group (an alcoholic hydroxyl group and a phenolic hydroxyl group) and an amino group are blocked with a compound capable of leaving. Examples of the organic group blocked with a compound from which an amino group can be removed include a ketimine group and an oxazoline group obtained by reacting an amino group with a ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone).

Compound (β-2) capable of reacting with an active hydrogen group
Examples thereof include polyisocyanates, polyepoxides, polycarboxylic acids, polyanhydrides, and polyacid halides. Among these, preferred are polyisocyanates and polyepoxides.

Examples of the polyisocyanate include those similar to the above-mentioned polyisocyanate (3), and preferred ones are also the same.

Examples of polyepoxides include polyglycidyl ethers (ethylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether,
Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, phenol novolak glycidyl etherate, etc.); diene oxides (pentadiene dioxide,
Hexadienedioxide, etc.). Preferred among these are polyglycidyl ethers.

Examples of the polycarboxylic acids include those similar to the above-mentioned polycarboxylic acid (2), and preferred ones are also the same.

Examples of the polycarboxylic acid anhydride include pyromellitic anhydride. 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 (β-2). Examples of the reaction terminator include monoisocyanates (lauryl isocyanate, phenyl isocyanate, etc.), monoepoxides (butyl glycidyl ether, etc.), monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.); those obtained by blocking monoamines (ketimine compounds, etc.) Monool (methanol, ethanol, isopropanol, butanol, phenol; monomercaptan (butyl mercaptan, lauryl mercaptan, etc.);

The ratio of the extender and / or the cross-linking agent (β) depends on the number of moles of the reactive group [α] in the reactive group-containing prepolymer (α) and the active hydrogen group [β] in (β). Ratio of moles of
[α] / [β] is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, and more preferably 1.2 / 1.
１ ／ 1 / 1.2. When (β) is water, water is 2
Treated as a multivalent active hydrogen compound.

The prepolymer (α) is a polyester,
Prepolymers such as epoxy resins and polyurethanes are included. Epoxy resins include addition condensation products of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) and epichlorohydrin. Examples of the polyurethane include a polyadduct of the polyol and the polyisocyanate.

The method for incorporating a reactive group into polyester, epoxy resin, polyurethane, etc. is as follows: a method in which one of the components is used in excess so that the functional group of the component remains at the terminal; And a method of reacting a compound containing a reactive group with a functional group.

According to the above method, 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 (1) to the polycarboxylic acid (2) is such that the molar ratio of the hydroxyl group [OH] to the carboxyl group [COOH] is [OH] / [COOH]. ], Usually 2/1 to 1/1, preferably 1.5 / 1 to 1 /
1, more preferably 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.

By reacting a polyisocyanate with the preprimer obtained in the above method, an isocyanate group-containing prepolymer is obtained, and by reacting a blocked polyisocyanate, a blocked isocyanate group-containing prepolymer is obtained. 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 polyisocyanate (3),
The same applies to preferred ones.

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 number of reactive groups per molecule in the prepolymer (α) is usually one or more, preferably 1.5 to 3 on average, and more preferably 1.8 to 2.5 on average.
Individual. When the content is within the above range, the molecular weight of the elongation and / or cross-linking reaction product of (α) increases. The number average molecular weight of (α) is usually 500 to 30,000, preferably 1,000 to 20,000, and more preferably 2,000.
0 to 10,000. The weight average molecular weight of (α) is
1,000-50,000, preferably 2,000-4
000, more preferably 4,000 to 20,000.
0. The melt viscosity of (α) at 100 ° C. is generally 2,000 poise or less, preferably 1,000 poise or less. It is preferable to use 2,000 poise or less in that resin particles having a sharp particle size distribution can be obtained with a small amount of solvent.

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

The elongation and / or crosslinking reaction time depends on the reactive group structure of the prepolymer (α),
Or it is selected depending on the reactivity of the combination of the crosslinking agents (β), but is usually 10 minutes to 40 hours,
24 hours. The reaction temperature is generally 0-150C, preferably 50-120C. 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.

Further, together with the prepolymer (α),
When (α) and (β) are reacted in an aqueous medium, a polymer (so-called dead polymer) that does not react with (α) and (β) can be contained in the system. That is, a resin which has not been subjected to an elongation reaction or a cross-linking reaction can be contained together with a resin which has been subjected to an elongation reaction and / or a cross-linking reaction of the prepolymer (α) in an aqueous medium.

In the present invention, the Tg, molecular weight, SP value and molecular weight between crosslinking points of the resin formed by elongation and / or cross-linking reaction of (α) and (β) have different preferable ranges depending on the application, and may be appropriately adjusted. I just need.

In the present invention, when forming the colored resin particles, other known additives may be used depending on the application. Examples of the additives include a filler, an antistatic agent, a colorant, a release agent, a charge control agent, an ultraviolet absorber, and an antioxidant. The above-mentioned other additives may be mixed at the time of forming a dispersion in an aqueous medium, but after previously mixing (α) and the additives, the mixture was added and dispersed in an aqueous medium. More preferred. In the present invention, the additives do not necessarily need to be mixed when forming the particles in the aqueous medium, and may be added after the particles are formed. For example, after forming particles containing no coloring agent, a coloring agent can be added by a known dyeing method.

The colored resin particles of the present invention are 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, and a circulating 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.

[0070]

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 [Dispersant (A-1) Having Phosphate Group] Into an autoclave equipped with a stir bar and a thermometer, 50 parts of methanol and 50 parts of xyltoluene were charged, and 2-hydroxyethyl (meta) was added. ) Acryloyl phosphate / methyl methacrylate / styrene (10% by weight / 50% by weight)
/ 40 wt% /) of 100 parts of a mixed monomer, 100 parts of methanol and 1 part of azobisisobutyronitrile
Drop polymerization was carried out at 4 ° C. for 4 hours. Devolatilize at normal pressure while raising the temperature to 120 ° C., switch to reduced pressure when the temperature reaches 120 ° C., perform devolatilization under reduced pressure over 2 hours,
A dispersant (A-1) having a phosphate group having a number average molecular weight of 3,200 and a weight average molecular weight of 9,400 was obtained.

Production Example 2 Synthesis of [Acrylic / Styrene Resin (B-1)] Into an autoclave equipped with a stir bar and a thermometer, 12 parts of xylene was charged, and glycidyl methacrylate / methyl methacrylate / styrene / acrylic acid was added. 100 parts of a mixed monomer of 2-ethylhexyl (25% by weight / 33% by weight / 40% by weight / 2% by weight) and 0.1 part of cumyl peroxide were subjected to drop polymerization at 170 ° C for 3 hours. Devolatilize at normal pressure while increasing the temperature to 180 ° C;
When the pressure became, the pressure was switched to reduced pressure, and devolatilization was performed under reduced pressure over 2 hours to obtain a resin (B-1) having a number average molecular weight of 10,500 and a weight average molecular weight of 120,000.

Production Example 3 [Synthesis of low molecular weight polyester (B-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 4 [Synthesis of Isocyanate Group-Containing Prepolymer (a-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 381 parts of a propylene oxide 2 mol adduct, 200 parts of isophthalic acid, 127 parts of terephthalic acid and 2 parts of dibutyltin oxide are added.
Reaction at 230 ° C. for 8 hours at normal pressure, and further 10-15 mm
After reacting for 5 hours while dehydrating under a reduced pressure of Hg, the mixture was cooled to 80 ° C., and reacted with 110 parts of isophorone diisocyanate in ethyl acetate for 2 hours to give a number average molecular weight of 3,20.
0, weight average molecular weight 12,000, NCO content 1.02
% Isocyanate group-containing prepolymer (a-1-1)
To give an ethyl acetate solution (solid concentration 75%).

Production Example 5 [Synthesis of Ketimine Compound (Blocked Amine: β-1)] 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 heated at 50 ° C. for 5 hours. After the reaction, the ketimine compound (β-
1) was obtained.

Example 1 [Synthesis of colored resin particles (1)] Resin (B) described in Production Example 2
-1) 100 parts, phthalocyanine blue 5 parts, phosphate group-containing dispersant (A-1) described in Production Example 1 as a dispersant
After mixing 2 parts and 230 parts of ethyl acetate, 350 parts of zirconia beads (particle size: 0.8) were added, and dispersed for 2 hours with a Glen Mill (manufactured by Asada Iron Works) to obtain [Pigment Dispersion (1)]. Was. 200 parts of ion-exchanged water in a beaker,
Hydroxyapatite 10% suspension (Nippon Chemical Industry
35 parts of Superitite 10) and 0.1 part of sodium dodecylbenzenesulfonate were added and uniformly dissolved. Then, the temperature was adjusted to 20 ° C and 5,000 with a TK homomixer.
While stirring at rpm, 100 parts of the above-mentioned pigment dispersion was added and stirred for 10 minutes. Then, the mixed solution was transferred to a kolben equipped with a stirring rod and a thermometer, heated to 50 ° C., and the solvent was removed under reduced pressure. After filtration, the cake was dispersed and washed in 450 parts of 5% hydrochloric acid, and filtered again. This operation was repeated with 5% hydrochloric acid 2
Once with 00 parts, once with 200 parts of 5% sodium hydroxide,
After repeating three times with 250 parts of ion-exchanged water, drying with a normal air dryer and air classification were performed to obtain [colored resin particles (1)] having a particle size d50 of 20 μm.

Example 2 [Synthesis of Colored Resin Particles (2)] 100 parts of ethyl acetate solution of isocyanate group-containing prepolymer (a-1) described in Production Example 4, 5 parts of permanent red 4R, Disper byk- as a pigment dispersant 111 (manufactured by BYK Japan: phosphate ester of ethylene glycol / polycaprolactone block copolymer, number average molecular weight 700,
Except that 2 parts by weight average molecular weight of 2,200) and 350 parts of ethyl acetate were used, all operations were the same as in Example 1,
[Pigment dispersion liquid (2)] and [colored resin particles (2)] having a particle diameter d50 of 20 μm were obtained. In this case, water becomes the elongating agent.

Production Example 3 [Synthesis of Colored Resin Particles (3)] 100 parts of the low-molecular-weight polyester (B-2) described in Production Example 3, 20 parts of an ethyl acetate solution of benzidine yellow (concentration: 20%), and a pigment dispersant After mixing 2 parts of Texahole (manufactured by San Nopco Ltd .: triethanolamine salt of higher alkyl alcohol and polyol sulfate, number average molecular weight 900, weight average molecular weight 5,300) and 230 parts of ethyl acetate,
350 parts of zirconia beads (particle diameter: 0.8) were put in, dispersed in a Glen Mill (manufactured by Asada Tekko Co., Ltd.) for 2 hours, and 20 parts of an ethyl acetate solution of the above-mentioned isocyanate group-containing prepolymer (a-1) and a production example 1.2 parts of the ketimine compound (β-1) described in 5 was mixed to obtain [Pigment Dispersion (3)]. Except for using this mixed dispersion, the same operation as in Example 1 was performed, and the particle size d50 was 20 μm.
[Colored resin particles (3)] were obtained.

Comparative Example 1 [Synthesis of Colored Resin Particles (4)] The pigment dispersant of Example 1 was replaced with "Dispalon DA-725" (manufactured by Kusunoki Kasei: polyester acid amide amine salt, acid value 20, amine value 48, number average) (Pigment dispersion liquid (4)) and [Colored resin particles (4)] having a particle diameter d50 of 20 μm, except that the molecular weight was changed to 1,100 and the weight average molecular weight was 4,200. I got

Comparative Example 2 [Synthesis of Colored Resin Particles (5)] The pigment dispersant of Example 2 was prepared by using "Dispalon DA-725" (manufactured by Kusunoki Chemical Co., Ltd .: polyester amide amine salt, acid value 20, amine value 48, number average). Except for changing the molecular weight to 1,100 and the weight average molecular weight to 4,200), the same operation as in Example 2 was carried out to obtain [Pigment Dispersion (5)] and [Colored Resin Particles (5)] having a particle size d50 of 20 μm. I got

Comparative Example 3 [Synthesis of Colored Resin Particles (6)] The pigment dispersant of Example 3 was prepared using "Dispalon DA-725" (manufactured by Kusunoki Kasei: polyester acid amide amine salt, acid value 20, amine value 48, number average). The same operation as in Example 3 was carried out except that the molecular weight was changed to 1,100 and the weight average molecular weight was 4,200) [Pigment dispersion liquid (6)] and [Colored resin particles (6)) having a particle diameter d50 of 20 μm. I got

Physical property measurement example 1 [Pigment dispersion liquid (1)] to [Pigment dispersion liquid (3)] and [Pigment dispersion liquid (4)] to [Pigment] obtained in Examples 1 to 3 and Comparative examples 1 to 3 Dispersion (6)] (particle size d)
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.). Further, each dispersion was heated at 30 ° C. and 50 ° C.
And the same measurement was performed after 24 hours and 48 hours. Tables 1 and 2 show the evaluation results. Pigment particle size is small,
The lower the aggregate content, the better the pigment dispersibility and the stability over time of the pigment dispersion state.

Physical property measurement example 2 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 long.
× 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 3 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.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

The colored resin particles of the present invention have good pigment dispersibility in the resin particles and have excellent color sharpness and transparency of the coating film obtained. 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] 0005

[Correction method] Change

[Correction contents]

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, the dispersant (A) having a functional group selected from the group consisting of a phosphoric acid (salt) group, a sulfonic acid (salt) group, and a sulfuric acid (salt) group
May be a low molecular weight compound or a high molecular weight compound, but preferably has a weight average molecular weight of 1000 to 500,000 by gel filtration chromatography (GPC) from the viewpoint of dispersion stability and compatibility with the resin (B). Preferably it is 1500-300,000. The phosphoric acid (salt) group, sulfonic acid (salt) group and sulfuric acid (salt) group function as adsorption sites for the pigment. Phosphoric acid (salt) groups include those partially converted into alkyl (C1-20) esters.
Salts include alkali metal salts (such as lithium salts, sodium salts, and potassium salts), alkaline earth metal salts (such as magnesium and calcium salts), and amine salts (such as trimethylamine, triethylamine, triethanolamine, dimethyloctylamine, and dimethyllauryl). Amines, dimethylaminoethanol, aminomethylpropanol, pyridine, ethylenediamine, etc.), ammonium salts and the like. When the dispersant (A) is a polymer compound (including an oligomer), the main skeleton thereof is selected from the group consisting of (co) polymers of vinyl monomers, polyethers, polyesters, and copolymers thereof. preferable. The content of phosphoric acid (salt) group, sulfonic acid (salt) group or sulfuric acid (salt) group (molecular weight g / equivalent) in the dispersant (A) is usually 2%.
It is from 2000 to 20000, preferably from 400 to 5000.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

In the above, as the compound having one or more active hydrogen groups at the terminal, 1 to 3 having 6 to 32 carbon atoms may be used.
And polyhydric alcohols, polyethers, polyesters (polycondensation type aliphatic polyesters and aromatic polyesters, and polycaprolactone). 6 to 3 carbon atoms
2 to 3 alcohols such as hexanol, octanol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, benzyl alcohol, 1,6-hexanediol, 1,8-octanediol, etc. Is mentioned. Examples of the polyether include a polyalkylene ether glycol having a weight average molecular weight of 100 to 10,000 (polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); an alicyclic diol having 5 to 18 carbon atoms (1,4-cyclohexanediene). Methanol, hydrogenated bisphenol A
) Or an adduct of an alkylene oxide having 2 to 18 carbon atoms (such as ethylene oxide, propylene oxide, butylene oxide, α-olefin oxide) of a bisphenol having 12 to 23 carbon atoms (such as bisphenol A, bisphenol F, and bisphenol S). (The number of moles to be added is 2 to 20).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 9/09 G03G 9/08 365 9/08 365 361 9/087 381 (72) Inventor Hidetoshi Noda Kyoto City East 11F, No.1, Nobashicho, Yamaku Sanyo Kasei Kogyo Co., Ltd. F term (reference) 2H005 AA01 AA06 AA21 AB03 CA02 CA07 CA08 CA15 CA17 CA21 EA06 EA07 4F070 AA13 AA15 AA32 AA46 AA47 AA52 AA53 AA72 AA77 FC04 DA05 AA03X BB01W CD00W CF00W CF00X CF19X CH02X CK02W FD096 FD20X 4J034 CA11 CE01 JA41 JA42 MA01 MA03 MA22 MA24

Claims (9)

[Claims] 1. A dispersant (A) in which a colorant (C) in a resin (B) has a functional group selected from the group consisting of a phosphoric acid (salt) group, a sulfonic acid (salt) group and a sulfuric acid (salt) group. Colored resin particles dispersed by the following. 2. The main skeleton of the dispersant (A) is a (co) polymer of a vinyl monomer, a polyether, a polyester,
The dispersant (A) has a weight average molecular weight of 1,000 to 500,000 as determined by gel filtration chromatography (GPC), which is selected from the group consisting of polyester, polycaprolactone and copolymers thereof. Colored resin particles. 3. The amount of the dispersant (A) is 10% of the colorant (C).
1 to 150 parts by weight with respect to 0 parts by weight, and the resin (B)
The amount is 0.01 to 90 parts by weight based on 100 parts.
Or the colored resin particles according to 2. 4. The colored resin particles according to claim 1, wherein said resin (B) is a resin selected from the group consisting of a polyurethane resin, an epoxy resin, a vinyl resin and a polyester resin. 5. The pigment according to claim 1, wherein the colorant (C) 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. A resin in which a colorant (C) is dispersed by a dispersant (A) having a functional group selected from the group consisting of a phosphoric acid (salt) group, a sulfonic acid (salt) group and a sulfuric acid (salt) group. (B)
Is dissolved or dispersed in an organic solvent, and the dissolved or dispersed liquid is emulsified or dispersed in an aqueous medium, followed by granulation. 7. A resin in which a colorant (C) is dispersed by a dispersant (A) having a functional group selected from the group consisting of a phosphoric acid (salt) group, a sulfonic acid (salt) group and a sulfuric acid (salt) group. (B)
Is dissolved or dispersed in an organic solvent, and the dissolved or dispersed liquid is emulsified in an aqueous medium containing an extender and / or a crosslinking agent (β). Or disperse, and (α) is extended and / or
Alternatively, a method for producing colored resin particles, comprising forming a resin (B) by crosslinking and granulating. 8. The reactive group of the prepolymer (α) is a reactive group selected from the group consisting of an isocyanate group, a blocked isocyanate group and an epoxy group, and the (β) has active hydrogen. Or the compound (β-1) generated. 9. The method according to claim 8, wherein (β-1) is water or a ketimine compound.