JP2002249591A - Process for producing resin composition particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing resin composition particles wherein a pigment is well dispersed and which give a resin film excellent in color sharpness and transparency. SOLUTION: In a process for producing resin composition particles by granulating an aqueous dispersion obtained by mixing a dispersion liquid (I) comprising an organic solvent (C) containing a resin (A) and a pigment (B) with aqueous medium containing a dispersant (D), the dispersion liquid (I) comprises a liquid preparation which is obtained by mixing an dispersing the resin (A), the pigment (B), the organic solvent (C) and, if necessary, a pigment dispersant (E) in a mixer having a function of revolving around and on its axis to give a mixture dispersion having a solid content of 50-98 wt.% and, if necessary, diluting this dispersion with an organic solvent and which has a solid content of 20-70%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing resin composition particles. More specifically, powder coatings, resin for hot-melt molding, spacers for manufacturing electronic components,
The present invention relates to a method for producing resin composition particles useful for toners and other molding materials.

[0002]

2. Description of the Related Art 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.
No. 3361 discloses a dry toner production method in which a pigment is dispersed in a resin by melt-kneading, and then dissolved in a solvent to prepare a toner preparation liquid. To obtain resin particles containing a pigment by volatilization of the resin.

[0003]

However, the above method is
Although the pigment dispersibility immediately after the melt-kneading is good, secondary disaggregation of the pigment occurs when the melt-kneaded product is dissolved in a solvent. Therefore, the pigment dispersibility of the obtained resin particles is not necessarily good. Are inferior in color sharpness and transparency. The present invention has been made in view of the above circumstances in the related art. That is, it is an object of the present invention to provide resin composition particles having good pigment dispersibility, excellent color sharpness and transparency of a resin film obtained, and excellent heat melting property and powder fluidity.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention. That is, the present invention provides an aqueous dispersion prepared by mixing a dispersion (I) in an organic solvent (C) containing a resin (A) and a pigment (B) with an aqueous medium containing a dispersant (D). In the method of producing resin composition particles by granulating, (I)
(B), (C) and, if necessary, a pigment dispersant (E) are mixed and dispersed by a mixer having a rotation and revolution function, and a mixed dispersion having a solid content of 50 to 98% by weight is diluted with an organic solvent, if necessary. A method for producing resin composition particles (1st invention), characterized in that it is an adjusted liquid having a solid content concentration of 20 to 70%; and an organic solvent (C) containing resin (A) and pigment (B). In a method for producing a resin composition particle by granulating an aqueous dispersion obtained by mixing an aqueous medium containing a dispersion liquid (I) and a dispersant (D) therein, (I) is characterized in that (A) A reactive group-containing prepolymer (a-1) which is a precursor,
(B), (C) and, if necessary, a pigment dispersant (E) are mixed and dispersed by a mixer having a rotation and revolution function, and a mixed dispersion having a solid content of 50 to 98% by weight is diluted with an organic solvent, if necessary. It is an adjustment liquid having a solid concentration of 20 to 70%,
A method for producing resin composition particles, comprising: forming a resin (A) by curing (a-1) with a curing agent (a-2) when mixing (I) with an aqueous medium (No. 2 invention)
It is.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the resin (A) may be a thermoplastic resin or a thermosetting resin.
For example, vinyl resins, polyurethanes, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicone resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, and mixtures thereof can be used. Among these, vinyl resins, polyester resins, polyurethane resins, epoxy resins and mixtures thereof are preferred, more preferably vinyl resins, polyester resins, polyurethane resins and mixtures thereof, particularly preferably vinyl resins, polyester resins and These are mixtures.

Among the resins (A), preferred resins, that is, vinyl resins, polyester resins, polyurethane resins and epoxy resins will be described, but other resins can be used in the same manner. The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer.
The vinyl monomers include the following (1) to (10).

(1) Vinyl hydrocarbons: (1) -1) Aliphatic vinyl hydrocarbons: alkenes having 2 to 20 carbon atoms, for example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene , Dodecene, octadecene and other α-olefins; alkadienes having 4 to 20 carbon atoms, such as butadiene, isoprene, 1,4-pentadiene,
5-hexadiene and 1,7-octadiene. (1) -2) Alicyclic vinyl hydrocarbons: mono- and dicycloalkenes and alkadienes such as cyclohexene,
(Di) cyclopentadiene, vinylcyclohexene and ethylidenebicycloheptene; terpenes such as pinene, limonene and indene. (1) -3) Aromatic vinyl hydrocarbon (having 8 to 2 carbon atoms)
0): Styrene and its hydrocarbyl (alkyl,
Cycloalkyl, aralkyl and / or alkenyl) substituents such as α-methylstyrene, vinyltoluene,
2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene and trivinylbenzene; and vinylnaphthalene.

(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 such as (meth) acrylic acid, (anhydride) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester,
Crotonic acid, itaconic acid, monoalkyl itaconate, glycol monoether itaconate, citraconic acid, monoalkyl citraconic acid and cinnamic acid; and salts thereof.

(3) Sulfone group-containing vinyl monomers, vinyl sulfate monoesters and salts thereof: 2 carbon atoms
To 14 alkene sulfonic acids such as vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid; styrene sulfonic acid and its alkyl-substituted alkyl group having 1 to 24 carbon atoms such as α-methylstyrene sulfonic acid; (Hydroxy) alkyl (C1-8)-
(Meth) acrylate or (meth) acrylamide, for example, sulfopropyl (meth) acrylate, 2
-(Meth) acryloyloxyethanesulfonic acid, 3-
(Meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid and 3- (meth) acrylamide-
2-hydroxypropanesulfonic acid; alkyl (3 to 18 carbon atoms) (meth) allyl sulfosuccinate; poly (n = 2 to 30) oxyalkylene (2 to 4 carbon atoms)
Oxyethylene, oxypropylene, oxybutylene:
Mono (meth) acrylate sulfate [poly (n = 5 to 15) oxypropylene monomethacrylate sulfate, etc.]; and salts thereof.

(4) Phosphoric acid group-containing vinyl monomers and salts thereof: (meth) acryloyloxyalkyl (C1-C2
4) Phosphoric acid monoesters, for example, 2- (meth) acryloyloxyethyl phosphate and phenyl-2-acryloyloxyethyl phosphate; (meth) acryloyloxyalkane (C1-24) phosphonic acids, for example, 2-acryloyloxyethane Phosphonic acids and the like; and salts thereof.

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 [mono To trialkyl (C1-20) amine salts, etc.], quaternary ammonium salts [aliphatic amines (trimethylamine, triethylamine, etc.), alicyclic amines (N-methylpyrrolidine, N, N-dimethylpiperazine, etc.) and 4 of nitrogen heterocyclic aromatics (4-dimethylaminopyridine, N-methylimidazole, etc.)
And alkanolamine salts (monoethanolamine salt, diethanolamine salt, triethanolamine salt and the like).

(5) Hydroxyl group-containing vinyl monomer: Alkenol having 2 to 12 carbon atoms, for example, (meth) allyl alcohol, 1-buten-3-ol and 2-buten-1-ol; Alkenediol,
For example, 2-butene-1,4-diol; an aromatic vinyl monomer having a hydroxyl group, for example, hydroxystyrene; a hydroxyalkyl (meth) acrylate having 5 to 8 carbon atoms, for example, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate Alkenyl ethers having 3 to 30 carbon atoms, such as 2-hydroxyethylpropenyl ether and sucrose allyl ether;

(6) Nitrogen-containing vinyl monomer: (6) -1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth)
Acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate,
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 and their organic acids (1 to 1 carbon atoms) 20 aliphatic carboxylic acids, 1 carbon atom
To 20 aromatic carboxylic acids) or salts with inorganic acids (such as hydrochloric acid). (6) -2) Amide group-containing nonionic vinyl monomer:
(Meth) acrylamide, N-methyl (meth) acrylamide, N-butyl (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N, N'-methylene-bis (meth) acrylamide, cinnamic acid Amide, N, N-dimethyl (meth)
Acrylamide, N, N-dibenzyl (meth) acrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone and the like. (6) -3) Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene and the like. (6) -4) A quaternary ammonium cation group-containing vinyl monomer: (6) -1) [dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
Dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine, etc.] (methyl chloride, dimethyl sulfate,
Quaternized with a quaternizing agent such as benzyl chloride or dimethyl carbonate). (6) -5) Nitro group-containing vinyl monomer: nitrostyrene and the like.

(7) Epoxy group-containing vinyl monomers: glycidyl (meth) acrylate and the like.

(8) Halogen-containing vinyl monomers: vinyl chloride, vinyl bromide, vinylidene chloride, (meth) allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, fluorinated Olefin (C2
-10, F1-20), fluorinated alkyl (2 to 2 carbon atoms)
10, F1-20) (meth) acrylate and the like.

(9) Vinyl esters: esters of unsaturated alcohols [vinyl, (meth) acrylic, isopropenyl, etc.] or hydroxystyrene with mono- or polycarboxylic acids having 1 to 12 carbon atoms, for example, vinyl acetate, vinyl butyrate Rate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, methyl-4-vinyl benzoate, vinyl methoxy acetate, vinyl benzoate and acetoxystyrene; unsaturated carboxylic acid alcohol (1 carbon atom)
30) esters such as 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, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, ethyl-α-ethoxy (meth) acrylate, di (cyclo) alkyl fumarate (two The alkyl group of
A straight-chain or branched-chain group having 2 to 8 carbon atoms) and di (cyclo) alkyl maleate (two alkyl groups are a straight-chain or branched-chain group having 2 to 8 carbon atoms) Polyhydric (2-3) alcohol unsaturated carboxylic acid esters such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and Polyethylene glycol di (meth) acrylate; degree of polymerization 5
50 polyoxyalkylene (C2-4) mono or poly (2-3) all unsaturated carboxylic acid esters,
For example, vinyl monomers having a polyalkylene (C2-4) glycol chain [polyethylene glycol (degree of polymerization 7) mono (meth) acrylate, polypropylene glycol (degree of polymerization 9) mono (meth) acrylate, methyl alcohol 10 mol addition of ethylene oxide Things (meta)
Acrylate and lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate; (10) Other vinyl monomers: (10) -1) vinyl (thio) ether, for example, 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'-vinyloxydiethylether, vinyl 2-ethylmercaptoethylether, phenoxystyrene, poly (di-tetra) (meth) allyloxyalkanes (2-6 carbon atoms) [diaryloxyethane , Triaryloxyethane, tetraaryloxyethane,
Tetraallyloxypropane, tetraallyloxybutane,
Tetramethylallyloxyethane, etc.], divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, etc. (10) -2) Vinyl ketone, for example, vinyl methyl ketone,
Vinyl ethyl ketone, vinyl phenyl ketone and the like. (10) -3) Vinyl sulfone, for example, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide and the like. (10) -4) Isosinate-containing vinyl monomers such as isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate.

The (co) polymer of a vinyl monomer includes a polymer obtained by (co) polymerizing one or two or more of any of the above monomers (1) to (10).
Polyethylene, polypropylene, polystyrene, styrene-alkyl (C1-20) (meth) acrylate copolymer, styrene-butadiene copolymer, (meth) acrylate-alkyl (C1-20) (meth) acrylate Examples include a polymer, a styrene-acrylonitrile copolymer, and a styrene-maleic anhydride copolymer.

The vinyl resin can be synthesized by a known polymerization method such as suspension, emulsification, solution polymerization or the like of the above-mentioned monomer using a radical polymerization initiator. The polymerization temperature is usually from 10 to
The reaction temperature is 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 initiator are those of the type that generates free radicals to initiate polymerization, such as 2,2′-azobisisobutyronitrile (AIBN) and 2,2′-azobis- (2,4-dimethylvalero). Azo compounds such as nitrile) (AVN); dibenzoyl peroxide, dicumyl peroxide, and other peroxides or persulfates, perborate, persuccinic acid described in JP-A-61-76517. Etc. can be used. The used amount of the polymerization initiator is 0.01 to 20%, preferably 0.05 to 10% based on the total amount of the monomers. A polymerization solvent may be used during the reaction, and aromatic hydrocarbon solvents (toluene, xylene, etc.), ester solvents (ethyl acetate, butyl acetate, etc.),
Ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (ethanol, isopropanol, etc.) and the like can be used.

Examples of the polyester resin include condensed polyesters, polylactones obtained by ring-opening polymerization of lactones, low molecular weight diols and lower alcohols (eg, methanol).
And a polycarbonate obtained by reacting the above with a carbonic acid diester. Examples of the condensed polyester include a polyol (e) and a polycarboxylic acid or an ester-forming derivative thereof (an acid anhydride, a lower alkyl ester, etc.) (f)
And the like. As (e), diol (e-1) and trivalent or higher valent polyol (e-2), etc.
Examples of (f) include dicarboxylic acid (f-1), trivalent or higher polycarboxylic acid (f-2), and acid anhydrides or lower alkyl esters thereof. The ratio of the polyol to the polycarboxylic acid is such that the hydroxyl group [OH] and the carboxyl group [C
The equivalent ratio of [OH] / [COOH] is usually 1.
5/1 to 1 / 1.5, preferably 1.4 / 1 to 1/1.
4, more preferably 1.3 / 1 to 1 / 1.3.

As (e-1), alkylene (C2-20) glycol (ethylene glycol, 1,2-
Propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, etc.); alkylene (C2-6) ether glycol (diethylene glycol) ,
Triethylene glycol, dipropylene glycol, polyethylene glycol (degree of polymerization 5 to 100), polypropylene glycol (degree of polymerization 5 to 100), polytetramethylene ether glycol (degree of polymerization 5 to 100), and the like;
Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S)
AO of the alicyclic diol [C2-4: ethylene oxide (EO), propylene oxide (P
O), butylene oxide, etc.]
10); AO of the above bisphenols (C2-4:
EO, PO, butylene oxide, etc.) adducts and the like. In the above and below, AO represents an alkylene oxide. Of these, preferred are those having 2 to 1 carbon atoms.
AO of alkylene glycol and bisphenol 2
The adduct is particularly preferable, and an AO adduct of a bisphenol and a combination thereof with an alkylene glycol having 2 to 12 carbon atoms are preferable. (E-2) includes polyhydric aliphatic alcohols having 3 to 8 or more valences (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trisphenols (trisphenol PA, etc.); Resin (phenol novolak, cresol novolak, etc.); AO adduct of the above trisphenols; AO adduct of the above novolak resin. Among these, preferred are polyhydric aliphatic alcohols having 3 to 8 or more valences and AO adducts of novolak resins, and particularly preferred are AO adducts of novolak resins.

(F-1) is a C4-C36 alkylenedicarboxylic acid (succinic acid, adipic acid, sebacic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, a branched alkylene having 8 or more carbon atoms) C4 to C36 alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); C8 to C36 alkyl succinic acid (decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid, etc.);
Alkenyl succinic acids (dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.); dimer acids and the like. . Among these, preferred are those having 4 to 20 carbon atoms.
And an aromatic dicarboxylic acid having 8 to 20 carbon atoms. (F-2) has 9 carbon atoms
To 20 aromatic polycarboxylic acids (such as trimellitic acid and pyromellitic acid). In addition, as (f-1) or (f-2), the above-mentioned acid anhydride or lower alkyl ester (eg, methyl ester, ethyl ester, isopropyl ester) may be used.

Examples of the polyurethane resin include polyisocyanate (g) and an active hydrogen group-containing compound (water, polyol (h), dicarboxylic acid (f-1), trivalent or higher polycarboxylic acid (f-2), polyamine ( i), polythiol (j), reaction terminator (monoamine, monol, etc.), etc.
And the like. For the polyaddition reaction, a known polyaddition reaction catalyst or the like can be used.

Examples of the polyisocyanate (g) include an aromatic polyisocyanate having 6 to 20 carbon atoms (excluding the carbon in the NCO group, the same applies hereinafter), an aliphatic polyisocyanate having 2 to 18 carbon atoms, and a 4 to 15 carbon atoms. Alicyclic polyisocyanate, araliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group,
Buret groups, uretdione groups, uretimine groups, isocyanurate groups, oxazolidone group-containing modified products, etc.) and mixtures of two or more of these. Specific examples of the aromatic polyisocyanate include 1,3- and / or
Or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TD
I), crude TDI, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), crude MD
I [crude diaminodiphenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (for example,
20%) of a mixture with a trifunctional or higher polyamine]: polyallyl polyisocyanate (PAP
I)], 1,5-naphthylene diisocyanate, 4,
4 ', 4 "-triphenylmethane triisocyanate,
m- and p-isocyanatophenylsulfonyl isocyanate; Above and below,% indicates% by weight. Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate (HD
I), 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, Examples thereof include aliphatic polyisocyanates such as 2-isocyanatoethyl-2,6-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 (TMXDI) and the like. The modified polyisocyanate includes modified MDI (urethane-modified MD).
I, 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 [eg, combined use of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)] Is included. Among these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI and MDI. , HD
I, hydrogenated MDI and IPDI.

The polyol (h) includes a low molecular polyol (h-1), a high molecular polyol [polyoxyalkylene polyol (h-2), a polyester polyol (h-3), a polymer polyol (h-4), Polybutadiene polyol (h-5), castor oil-based polyol (h
-6), acrylic polyol (h-7), etc., number average molecular weight: usually 500 to 20,000, preferably 500 to 1
000, more preferably 1,000 to 3,000]
And the like. In addition, the number average molecular weight (Mn) and the weight average molecular weight (Mw) in the above and below are measured by gel permeation chromatography (GPC) (THF solvent, reference substance polystyrene).

(H-1) includes polyhydric alcohols having 2 to 8 valences (h-1-1), and AO (E
O, PO, 1,2-, 1,3-, 2,3- or 1,
4-butylene oxide, α-olefin oxide,
Styrene oxide, epichlorohydrin, etc.) adducts (Mn less than 500), polyhydric phenols (h-1-2)
AO adducts (Mn less than 500), phosphorus-based polyols and the like.

(H-1-1) includes ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, neopentyl Dihydric alcohols such as glycol, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, and 2,2-bis (4,4′-hydroxycyclohexyl) propane; Trihydric alcohols such as pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylitol, mannitol,
Dipentaerythritol, glucose, fructose,
Examples thereof include 4- to 8-valent alcohols such as sucrose.

(H-1-2) includes pyrogallol,
Polyhydric phenols such as catechol and hydroquinone; and bisphenols such as bisphenol A, bisphenol F and bisphenol S. Examples of the phosphorus-based polyol include AO adducts (Mn less than 500) such as phosphoric acid, phosphorous acid, and phosphonic acid.

Examples of (h-2) include compounds having a structure in which AO is added to an active hydrogen atom-containing polyfunctional compound, and a mixture of two or more of these compounds.

As the active hydrogen atom-containing polyfunctional compound,
(H-1-1), (h-1-2), amines (h-2-
1), polycarboxylic acid (f), phosphoric acid (h-2-
2) and polythiol (h-2-3).

(H-2-1) includes ammonia, alkylamines having 1 to 20 carbon atoms (such as butylamine),
Monoamines such as aniline and polyamine (i) described below
Is mentioned.

Examples of (h-2-2) include phosphoric acid, phosphorous acid, phosphonic acid and the like. Examples of (h-2-3) include polyvalent polythiol compounds obtained by reacting a glycidyl group-containing compound with hydrogen sulfide. The active hydrogen atom-containing compounds described above may be used in combination of two or more.

AO added to a compound containing an active hydrogen atom
(C 2-12) include EO, PO, 1,2-,
2,3- or 1,3-butylene oxide, tetrahydrofuran (THF), styrene oxide, α-olefin oxide, epichlorohydrin and the like.

AO may be used alone or in combination of two or more.
In the latter case, a mixed system of both block addition (chip type, balance type, active secondary type, etc.) and random addition [chip after random addition: 0 to 50% of EO chains arbitrarily distributed in the molecule ( Preferably 5 to 40
%) And 0 to 30% (preferably 5 to 25%) EO
Chain with a chip at the molecular end]. Of these AOs, preferred are EO alone, PO alone, TH
F alone, combined use of PO and EO, combined use of PO and / or EO with THF (in the case of combined use, random, block, or a mixture of both).

The addition of AO to the compound containing an active hydrogen atom can be carried out by a conventional method, and can be carried out without a catalyst or in the presence of a catalyst (alkali catalyst, amine catalyst, acidic catalyst) (especially in the latter half of AO addition). In one or more stages under normal pressure or under pressure.

The polyoxyalkylene polyol (h-2) may be reacted with a small proportion of polyisocyanate (described later) to further increase the molecular weight (polyoxyalkylene polyol / h). Equivalent ratio of polyisocyanate: for example, usually 1.2 to 10/1, preferably 1.5 to 2/1).

Equivalent of (h-2) (Mn per hydroxyl group)
Is usually 100 to 10,000, preferably 250 to
It is 5,000, more preferably 500-1,500. The functionality of the polyoxyalkylene polyol is usually 2 to 8, preferably 2 to 3, and particularly preferably 2.

It is preferable that the degree of unsaturation of (h-2) is small, and it is usually 0.1 meq / g or less, preferably 0.05 mq / g or less.
eq / g or less, more preferably 0.02 meq / g or less. The primary hydroxyl group content of (h-2) is usually 0 to 100%, preferably 30 to 100%, more preferably 50 to 100%, and most preferably 70 to 100%.
%.

The polyester polyol (h-3) includes:
Condensed polyester diol obtained by reacting polyol (e) with polycarboxylic acid (f), polylactone diol obtained by ring-opening polymerization of lactone, polyol (e) and carbonic acid diester of lower alcohol (methanol or the like) And polycarbonate diol obtained by the reaction.

Specific examples of (h-3) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, and polybutylene hexamethylene adipate. Diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol, polycaprolactone diol or triol, polyhexamethylene carbonate diol And the like.

The hydroxyl value of (h-3) is usually from 10 to 30.
0, preferably 20 to 250, more preferably 30 to 2
00.

As the polymer polyol (h-4), a radical polymerizable monomer [the above-mentioned vinyl monomers (1) to (10), for example, styrene , (Meth) acrylonitrile, (meth) acrylic acid ester, vinyl chloride, and a mixture of two or more thereof], and the polymer is finely dispersed.

In order to polymerize these monomers, a radical polymerization initiator is usually used. The radical polymerization initiator used is the same as described above, and the amount used is also the same.

The polymerization reaction in the polyol can be carried out without solvent, but when the concentration of the polymer is high, it is preferable to carry out the reaction in the presence of an organic solvent. Examples of the organic solvent include benzene, toluene, xylene, acetonitrile, ethyl acetate, hexane, heptane, dioxane,
N, N-dimethylformamide, N, N-dimethylacetamide, isopropyl alcohol, n-butanol and the like can be mentioned. If necessary, the polymerization can be carried out in the presence of a known chain transfer agent (alkyl mercaptans, carbon tetrachloride, carbon tetrabromide, chloroform, enol ethers described in JP-A-55-31880). .

The polymerization can be carried out either batchwise or continuously. The polymerization reaction can be carried out at a temperature equal to or higher than the decomposition temperature of the polymerization initiator, usually 60 to 180 ° C, preferably 90 to 160 ° C, particularly preferably 100 to 150 ° C, under atmospheric pressure or under pressure, and even under reduced pressure. Can do it.

After the completion of the polymerization reaction, the resulting polymer polyol can be used as it is for the production of polyurethane without any post-treatment, but after the completion of the reaction, an organic solvent, decomposition products of a polymerization initiator and unreacted monomers are obtained. Impurities such as
It is desirable to remove by conventional means.

(H-4) thus obtained is usually 30
~ 70%, preferably 40-60%, more preferably 4%
It is a translucent to opaque white or tan dispersion of 5 to 55%, most preferably 50 to 55%, of the total polymerized monomers, i.e., the polymer, dispersed in a polyol.

The hydroxyl value of (h-4) is usually from 10 to 3
00, preferably 20-250, more preferably 30-
200.

Examples of the polybutadiene polyol (h-5) include those having a 1,2-vinyl structure, those having a 1,2-vinyl structure and a 1,4-trans structure, and those having a 1,4-trans structure. Things. 1,
The ratio of the 2-vinyl structure to the 1,4-trans structure can be varied, for example, from 100: 0 to 0:
100. Further, (h-5) includes homopolymers and copolymers (styrene butadiene copolymer, acrylonitrile butadiene copolymer and the like), and hydrogenated products thereof (hydrogenation rate: for example, 20 to 100%). The Mn of the (h-5) is usually from 500 to 10,000.
00.

As a specific example of (h-5), NISSO-PB G series (G-100 manufactured by Nippon Soda Co., Ltd.)
0, G-2000, G-3000, etc.), Poly Bd (Poly Bd R-45M, R-
45HT, CS-15, CN-15) and the like.

The castor oil-based polyol (h-6) includes castor oil and modified castor oil (such as castor oil modified with a polyol such as trimethylolpropane and pentaerythritol). Acrylic polyol (h
As -7), those obtained by copolymerizing a vinyl monomer having a hydroxyl group (for example, hydroxyethyl methacrylate) and another vinyl monomer (for example, methyl methacrylate, styrene, butyl acrylate) can be mentioned. The number of functional groups is usually 2-3, and the hydroxyl value is usually 10-15.
0.

Examples of the polyamine (i) include aliphatic polyamines (2 to 18 carbon atoms): aliphatic polyamines ア ル キ レ ン alkylene diamines having 2 to 6 carbon atoms (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, Hexamethylenediamine, etc.), polyalkylene (C2-6) polyamines [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]; (C1-4) or hydroxyalkyl (C2-4) substituted [dialkyl (C1-3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2, 5- Hexamethylene diamine, methyl iminobispropylamine, etc.]; heterocycle-containing aliphatic polyamines [3,9-bis (3-aminopropyl) -2,4,8,10-spiro [5,
5] undecane and the like]; aromatic ring-containing aliphatic amines (8 to 15 carbon atoms) (xylylenediamine, tetrachloro-p
-Xylylenediamine, etc.), alicyclic polyamines (having 4 to 15 carbon atoms): 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated diaminodiphenylmethane), etc. Heterocyclic polyamine (C4-15): piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2
Aromatic polyamines (C6-20) such as -methylpropyl) piperazine: unsubstituted aromatic polyamine [1,
2-, 1,3- and 1,4-phenylenediamine, 2,
4'- and 4,4'-diaminodiphenylmethane, crude diaminodiphenylmethane (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m -Aminobenzylamine, triphenylmethane-4,4 ',
4 "-triamine, naphthylenediamine and the like; aromatic polyamines having a nucleus-substituted alkyl group (alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n- and i-propyl and butyl), 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.) and mixtures of these isomers in various proportions; nuclear-substituted electron-withdrawing groups (Cl, Br,
Aromatic polyamines having halogens such as I and F; alkoxy groups such as methoxy and ethoxy; nitro groups, etc. [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylene Diamine, 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 polyamine having a secondary amino group [part or all of -NH2 of the above aromatic polyamine is -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: low molecular weight polyamide polyamine obtained by condensation of dicarboxylic acid (dimer acid, etc.) with excess (2 mol or more per mole of acid) polyamines (alkylene diamine, polyalkylene polyamine, etc.) Etc., polyether polyamines:
Examples include hydrides of cyanoethylated polyether polyols (such as polyalkylene glycol).

The polythiol (j) has 2 to 2 carbon atoms.
24 dithiols and 3 to 6 or more valent, 5 carbon atoms
~ 30 polythiols and the like can be used. Examples of the dithiol include ethylene dithiol, 1,4-butanedithiol, and 1,6-hexanedithiol. As the polythiol, for example, Capure 38
00 (manufactured by Japan Epoxy Resin Co., Ltd.) and polyvinyl thiol.

Examples of the epoxy resin include polyepoxide (k) and an active hydrogen group-containing compound {water, polyol [the diol (e-1) and the polyol (e-
2)], dicarboxylic acid (f-1), trivalent or higher polycarboxylic acid (f-2), polyamine (i), polythiol (j), etc.}, dicarboxylic acid (f-1) or trivalent or higher poly Examples include polyadducts of carboxylic acid (f-2) with acid anhydrides and the like.

The polyepoxide (k) is not particularly limited as long as it has two or more epoxy groups in the molecule.
Preferred as (k) is one having from 2 to 6 epoxy groups in the molecule from the viewpoint of the mechanical properties of the cured product. Epoxy equivalent of (k) (M per epoxy group
n) is usually 65 to 1000, preferably 90
~ 500. When the epoxy equivalent exceeds 1000,
The crosslinked structure becomes loose, and the physical properties such as water resistance, chemical resistance, and mechanical strength of the cured product are deteriorated.
It is difficult to synthesize less than 5.

Examples of (k) include aromatic polyepoxides, heterocyclic polyepoxides, alicyclic polyepoxides and aliphatic polyepoxides. Examples of the aromatic polyepoxide include glycidyl ethers of polyhydric phenols, glycidyl esters of aromatic polycarboxylic acids, glycidyl aromatic polyamines, and glycidylated aminophenols.

The 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 ether, Tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyldiglycidyl ether, octachloro-4,
4'-dihydroxybiphenyl diglycidyl ether,
Tetramethylbiphenyl diglycidyl ether, dihydroxynaphthyl cresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether,
Reaction of 2 moles of bisphenol A with 3 moles of epichlorohydrin Diglycidyl ether, phenol and glyoxal, glutaraldehyde, or polyphenol obtained by condensation reaction of formaldehyde (condensation degree 2 to 2)
0) polyglycidyl ether and polyglycidyl ether of polyphenol (condensation degree: 2 to 20) obtained by condensation reaction of resorcinol and acetone.
As glycidyl esters of aromatic polycarboxylic acids,
Examples include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate.

As the glycidyl aromatic amine, N, N
-Diglycidylaniline, N, N, N ', N'-tetraglycidylxylylenediamine, N, N, N', N'-
Examples thereof include tetraglycidyl diphenylmethane diamine, and triglycidyl ether of p-aminophenol.

Further, the aromatic polyepoxide has TD
A diglycidyl urethane compound obtained by addition reaction of I or MDI with glycidol, a glycidyl group-containing polyurethane prepolymer obtained by reacting a polyol with the two reactants, and an AO (2-4 carbon atoms) of a bisphenol (such as bisphenol A) : For example, EO and / or PO) adducts. Heterocyclic polyepoxides include trisglycidylmelamine.

Examples of the alicyclic polyepoxide include vinylcyclohexenedionoxide, limonenedoxide, dicyclopentadienedionoxide, and bis (2,3).
-Epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'
-Epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate and bis (3,4-epoxy-
6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester and the like. The alicyclic system also includes a nuclear hydrogenated product of the aromatic polyepoxide. Examples of the aliphatic polyepoxide include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of aliphatic polycarboxylic acids, and glycidyl aliphatic amines. As polyglycidyl ethers of polyhydric aliphatic alcohols, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether,
Polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerin polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, etc. Is mentioned. Examples of the polyglycidyl ester of an aliphatic polycarboxylic acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, and diglycidyl pimerate. 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 polyepoxides and aromatic polyepoxides are preferred. The polyepoxides of the present invention may be used in combination of two or more.

The Mw of the resin (A) is preferably from 1500 to 5,000,000, more preferably from 2,000 to 1,000,000,
Particularly preferably, it is 3,000 to 500,000. Resin (A)
Glass transition point (Tg: usually −50 ° C. to 200 ° C.), weight average molecular weight (normally 2 to 5,000,000), SP value (normally 7 to 18), and molecular weight between crosslinking points (normally 2 to 2,000,000 The Tg is determined by DSC (differential scanning calorimetry, heating rate 20 ° C./min), and the SP value is Polym.
er Engineering and Science
e, Feburary, 1974, Vol. 14, N
o. Calculated by the method described on pages 2,147-154.

Examples of the pigment (B) include white pigments, blue pigments, red pigments, yellow pigments, black pigments and the like. 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. Organic pigments include phthalocyanine, azo lake, monoazo, disazo, quinacridone, dioxazine, isoindolinone, thioindigo, perylene, quinophthalone, anthraquinone, carmine, naphthol, and pyrazolone. And dibromoanthrones. The kind of the pigment to be used varies depending on the intended use, and may be appropriately selected.

In order to perform the mixing and dispersing in a shorter time, the pigment (B) is mixed with the organic solvent (C) at a solid content of 5 to 50%.
(Preferably 10 to 40%), and coarse particles are coarsely pulverized in advance so that the volume average particle diameter is preferably in the range of 1 to 100 μm. The volume average particle size is measured by a laser type particle size distribution analyzer [for example, product name: LA-920]
(Manufactured by Horiba, Ltd.)]. For the method of coarse crushing, any known dispersion method may be used, and a batch disperser, a continuous disperser, a high-pressure disperser, a vibration disperser, an ultrasonic disperser, a media disperser, three Examples of the method include a roll mill and a ball mill. Among these, a continuous disperser, a high-pressure disperser, an ultrasonic disperser, and a media disperser are preferable from the viewpoint of shortening the dispersion time. Particularly preferably,
TK pipeline homomixer (manufactured by Tokushu Kika Kogyo),
Colloid mill (manufactured by Shinko Pantech), slasher,
Trigonal wet pulverizer (Mitsui Miike Kakoki Co., Ltd.), continuous disperser such as Capitron (Eurotec Co., Ltd.), Fine Flow Mill (Taikai Kiko Co., Ltd.), Microfluidizer (Mizuho Kogyo), Nanomizer ( High pressure dispersing machine such as ANP Gaurin (manufactured by Gaurin), ultrasonic dispersing machine such as ultrasonic homogenizer (manufactured by Branson), nanograin mill, basket mill, AD
A media type wet disperser such as a mill (manufactured by Asada Tekko Co., Ltd.) and the like can be mentioned.

The content of (B) is usually 0.1 to 50 parts, preferably 1 to 30 parts, relative to 100 parts of resin (A).
Particularly preferred is 2 to 20 parts. Above and below, parts mean parts by weight.

Known dyes, magnetic powders and the like can be used together with the above pigments. As the dye, anthraquinone dye (Slen Yellow GCN, Slen Brilliant Violet 2)
R), indigoid dyes (Indanthrene Brilliant Pink R, Suren Orange R, etc.), oil-soluble dyes (Oil Red, Sudan-I, etc.), azo dyes (Orange II,
And quinone imine dyes (such as rhodamine B). The content of the dye is usually 0 to 50 parts with respect to 100 parts of the resin (A).

As the magnetic powder, iron oxide [eg γ-Fe
_TwoO_Three(Γ-hematite)], CrO _Three(Black trioxide
), Alloy-based magnetic material [for example, Co-γ-Fe_TwoO_Three(Ko
Baltic ferrite or cobalt doped γ-iron oxide),
Fe-Co-Cr], pure iron Fe (metal powder), nitrogen
Iron oxide and iron carbide. The shape of the magnetic powder is usually
Granular and acicular. Example of size (μm) of magnetic powder
If shown, the diameter is usually 0.02-0.7, for example 0.2
~ 0.7, minor axis 0.02 ~ 0.1. Contains magnetic powder
The amount is usually 0 to 70 parts with respect to 100 parts of the resin (A).
is there.

When the resin (A), the pigment (B) and the organic solvent (C) are mixed and dispersed, a pigment dispersant (E) is used for the purpose of improving the dispersibility of the (B). preferable. Examples of (E) include a polymer type dispersant containing a polar group having adsorptivity to the pigment. The molecular weight of the dispersant is usually 1,000 to 1,000,000. Examples of the polar group having adsorptivity to the pigment include an acidic group such as a phosphoric acid group, a carboxylic acid group, a sulfonic acid group and a sulfamic acid group and a neutralizing base thereof, an amino group and a neutralizing base of an amino group,
And a quaternary ammonium base, an amide group and an imide group. Examples of the main skeleton of the polymer type dispersant include (co) polymers of vinyl monomers such as acrylates, styrene, and vinyl acetate, polyesters, and polyamide polyamines.

The vinyl monomers include the above-mentioned (1) to
(10), and as the (co) polymer of a vinyl monomer, any of the above (2) to (7) may be used alone or in combination of two or more with other vinyl monomers. Can be synthesized by a known polymerization method such as suspension, emulsification, or solution polymerization using a radical polymerization catalyst, and the production method is the same as described above.

Examples of the polyurethane include the above-mentioned polyisocyanate (g), an acidic group such as a phosphoric acid group, a carboxylic acid group, a sulfone group, a sulfamic acid group, an amino group or a phosphoric acid group and a neutralized salt thereof, and a quaternary ammonium base. And a polyaddition product with a polyester or the like.

Polyurethane includes: -1: a prepolymer having an NCO group obtained by reacting a polyisocyanate (g) with a polyol having two or more active hydrogen groups at a terminal (for example, a polyester di- or triol having an Mw of 200 to 100,000). The polymer is reacted with a compound having a tertiary amino group and one or more active hydrogen groups, and then neutralized with an organic acid. -2: reacting a compound having a tertiary amino group and one or more active hydrogen groups [eg, N, N-dialkyl (C1-6) alkanol (C2-6) amine] with polyisocyanate (g) The prepolymer having an NCO group is allowed to react with a polyol having two or more active hydrogen groups at terminals (for example, a polyester di or triol having a Mw of 200 to 100,000), and then neutralized with an organic acid. And the like.

As the polyamide polyamine, the above-mentioned polycondensates of the polyamine (i) and the polycarboxylic acid (f) can be used. Known polycondensation catalysts and the like can be used for the polycondensation reaction. The amount of (E) to be used is generally 0 to 100 parts with respect to 100 parts of the pigment (B).

Examples of the organic solvent (C) include hydrocarbon solvents (toluene, xylene, etc.), ester solvents (ethyl acetate, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), and mixed solvents of two or more thereof. No.

The amount of the organic solvent (C) is such that the solid content of the mixed dispersion {resin (A), pigment (B) and, if necessary, pigment dispersant (E)} is 50 to 98%, preferably 60 to 95%.
%, More preferably 65 to 90%. When the concentration is less than 50%, the shear required for dispersion is insufficient, and the disintegration speed of the secondary particles of the pigment (B) tends to be extremely low. When the concentration exceeds 98%, the viscosity at the time of dispersion increases, and the resin is retained in the dispersion system, so that the dispersion speed tends to be slow. The solid content concentration is 1% of the weight of the sample.
The ratio of the residue after drying at 50 ° C. for 45 minutes is represented by%. The temperature at the time of mixing and dispersion is usually 0 to 100 ° C, preferably 10 to 95 ° C.
° C, more preferably 20 to 90 ° C. The pressure at the time of mixing and dispersing is usually -0.1 to 1.0 MPa, preferably -0.
09 to 0.5 MPa, more preferably -0.01 to
0.1 MPa.

Resin (A), pigment (B), organic solvent (C)
When mixing and dispersing the pigment dispersant (E) as necessary, a mixer having a rotation and revolution function is used. The mixer having a rotation and revolving function refers to a mixer in which a stirring blade performs a rotation motion and a revolving motion, and crushes and disperses a solid material by a shear between the stirring blade and the bottom of the dispersion tank and the wall of the dispersion tank. A mixer having a rotation and revolving function has a high peripheral speed of the stirring blades and is efficient, so that the pigment can be dispersed in a short time. Examples of the mixer having a rotation and revolving function include a planetary mixer in which two or three stirring blades also perform revolving motion while rotating, a universal mixer in which one or two stirring blades perform revolving orbiting motion, and the like. As a more specific example, a planetary mixer PVM
Series (made by Asada Iron Works), Planetary Mixer PL
MV series (manufactured by Inoue Seisakusho), T.V. K. Hibismix, T.I. K. Hibis Dispermix (manufactured by Tokushu Kika Kogyo Co., Ltd.) and the like.

In order to obtain an emulsion or dispersion having a sharper particle size distribution, the mixed dispersion has a solid content of 20 to 7 before being mixed with an aqueous medium to form an emulsion or dispersion.
It is preferable to adjust with an organic solvent so as to be 0%, preferably 25 to 65%. Solid content concentration before adjustment is 50-7
When it is 0% and the viscosity by a Brookfield viscometer at 25 ° C. is 100 to 50,000 mPa · s, it can be used without adjustment with an organic solvent. The organic solvent used is the same as described above. The solid content concentration can be adjusted by stirring and mixing the mixed dispersion and the organic solvent. Adjustment temperature is usually 0 to 50 ° C, preferably 5 to 40 ° C.
° C, more preferably 10 to 30 ° C.

The proportion of (A) in the resulting preparation is usually 20 to 70%, preferably 22 to 68%, particularly preferably 24 to 67%, and the proportion of (B) is usually 0.2 to 35.
%, Preferably 0.3-33%, particularly preferably 0.5%
-30%, the proportion of (C) is usually 30-80%, preferably 31-78%, particularly preferably 33-76%, (D)
Is usually 0 to 15 parts, preferably 0.01 to 13 parts.
Parts, particularly preferably 0.1 to 10 parts.

The resin composition particles of the present invention can be obtained by mixing the obtained adjustment liquid and the aqueous medium as described below to obtain a dispersion and granulating the dispersion. As the aqueous medium, water alone may be used, but a solvent having a solubility in water of 5 or more may be used in combination. Solvents that can be used in combination include alcohols (methanol, isopropanol, ethylene glycol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), ester solvents (ethyl acetate, etc.), amide solvents (dimethylformamide, etc.), ether solvents ( Tetrahydrofuran, etc.) and cellosolve solvents (eg, methyl cellosolve). The amount of the solvent used is water 100
The amount is usually from 0 to 50 parts, preferably from 1 to 30 parts, per part.

At the time of dispersion, a dispersant (D) is used to control the particle size and maintain the dispersion stability of the dispersion.
As (D), known surfactants, aqueous polymers and the like can be used. Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and a combination of two or more of these.

As the anionic surfactant, carboxylic acid or a salt thereof, a sulfate salt, a salt of a carboxymethylated product, a sulfonate, a phosphate and the like are used.

The carboxylic acid or a salt thereof has 8 carbon atoms.
-22 saturated or unsaturated fatty acids or salts thereof, such as capric acid, lauric acid, myristic acid,
Mixtures of palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid and ricinoleic acid and higher fatty acids obtained by saponifying coconut oil, palm kernel oil, rice bran oil, tallow, etc. Examples of the salt include sodium salts, potassium salts, ammonium salts, and amine salts [mono- to trialkyl (having 1 to 2 carbon atoms).
0) amine salts, etc.], quaternary ammonium salts [aliphatic amines (trimethylamine, triethylamine, etc.), alicyclic amines (N-methylpyrrolidine, N, N-dimethylpiperazine, etc.) and nitrogen-containing heterocyclic aromatics (4 -Dimethylaminopyridine, N-methylimidazole and the like) and alkanolamine salts (monoethanolamine salt, diethanolamine salt, triethanolamine salt and the like).

The sulfates include higher alcohol sulfates (sulfates of aliphatic alcohols having 8 to 18 carbon atoms) and higher alkyl ether sulfates (AO (EO) of aliphatic alcohols having 8 to 18 carbon atoms). And / or PO) a sulfate ester salt of a 1 to 10 mol adduct), a sulfated oil (a natural unsaturated fat or oil having 12 to 50 carbon atoms or an unsaturated wax neutralized by sulfation as it is), sulfated Fatty acid esters (unsaturated fatty acids (C6
To 40) lower alcohols (1 to 8 carbon atoms) which are sulfated and neutralized and sulfated olefins (12 to 18 carbon atoms which are sulfated and neutralized)
Etc. can be used. Examples of the salt include a sodium salt, a potassium salt, an amine salt, an ammonium salt, a quaternary ammonium salt, and an alkanolamine salt (such as a monoethanolamine salt, a diethanolamine salt, and a triethanolamine salt).

The higher alcohol sulfates include:
For example, sulfuric acid of octyl alcohol sulfate, decyl alcohol sulfate, lauryl alcohol sulfate, stearyl alcohol sulfate, alcohol synthesized using a Ziegler catalyst (for example, trade name: ALFOL 1214: manufactured by CONDEA) Ester salts and alcohols synthesized by the oxo method (for example, trade names: Dovanol 23, 25, 45, Diadol 115-L, 115H, 135: manufactured by Mitsubishi Chemical Corporation; trade name: tridecanol: manufactured by Kyowa Hakko, trade name: (Oxocol 1213, 1215, 1415: manufactured by Nissan Chemical Industries, Ltd.).

The higher alkyl ether sulfates include, for example, sulfates of adduct of lauryl alcohol EO 2 moles and sulfates of 3 moles of octyl alcohol EO. Examples of the sulfated oil include castor oil, peanut oil, olive oil, rapeseed oil, salts of sulfated oxides such as tallow and sheep tallow, and the like. Examples of the sulfated fatty acid ester include salts of sulfates such as butyl oleate and butyl ricinoleate. Examples of the sulfated olefin include trade name: Teapol (manufactured by Shell).

The salts of carboxymethylated compounds include aliphatic alcohols having 8 to 16 carbon atoms (octyl alcohol,
Decyl alcohol, lauryl alcohol, dovanol 2
3, tridecanol, etc.) and a C10-C16 aliphatic alcohol AO (EO and / or PO) 1-10 mol adduct (octyl alcohol EO 3 mol adduct, lauryl alcohol EO 4 mol adduct) , A carboxymethylated salt of dodecanol 23EO 3 mol adduct and tridecanol EO 5 mol adduct) can be used.

As the sulfonic acid salt, alkyl benzene sulfonic acid salt, alkyl naphthalene sulfonic acid salt, sulfosuccinic acid diester salt, α-olefin sulfonic acid salt, sulfonic acid salt of Igepon T type and other aromatic ring-containing compounds can be used. Examples of the alkylbenzene sulfonate include sodium dodecylbenzenesulfonate.

The alkylnaphthalene sulfonate includes, for example, sodium dodecylnaphthalenesulfonate. Examples of the sulfosuccinic acid diester salt include di-2-ethylhexyl sulfosuccinate sodium salt. Examples of the sulfonate of the aromatic ring-containing compound include a mono- or di-sulfonate of an alkylated diphenyl ether and a styrenated phenol sulfonate.

As the phosphate ester salt, a higher alcohol phosphate ester salt and a higher alcohol EO adduct phosphate ester salt and the like can be used. Examples of higher alcohol phosphate ester salts include lauryl alcohol phosphate monoester disodium salt and lauryl alcohol phosphate diester sodium salt. As higher alcohol EO adduct phosphate ester salts, for example,
Oleyl alcohol EO 5-mol adduct phosphoric acid monoester disodium salt and the like.

As the cationic surfactant, a quaternary ammonium salt type surfactant, an amine salt type surfactant and the like can be used. As the quaternary ammonium salt type surfactant, a tertiary amine having 3 to 40 carbon atoms and a quaternizing agent (for example,
Alkylation agents such as methyl chloride, methyl bromide, ethyl chloride, benzyl chloride and dimethyl sulfate, and EO), for example, lauryl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, stearyl Examples include trimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), cetylpyridinium chloride, polyoxyethylenetrimethylammonium chloride, and stearamideethyldiethylmethylammonium methosulfate.

As the amine salt type surfactants, primary to tertiary amines are converted into inorganic acids (for example, hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, phosphoric acid and perchloric acid) or organic acids (acetic acid, formic acid, Oxalic acid, lactic acid, gluconic acid, adipic acid, 2 carbon atoms
24, such as alkyl phosphoric acid, malic acid and citric acid). Examples of the primary amine salt type surfactant include inorganic acid salts of aliphatic higher amines having 8 to 40 carbon atoms (eg, higher amines such as laurylamine, stearylamine, cetylamine, hardened tallowamine, and rosinamine). Or an organic acid salt and a higher fatty acid (C8-C40, stearic acid, oleic acid, etc.) salt of a lower amine (C2-6) are mentioned.

Examples of the secondary amine salt type surfactant include inorganic acid salts and organic acid salts such as EO adducts of aliphatic amines having 4 to 40 carbon atoms. Examples of the tertiary amine salt type surfactant include aliphatic amines having 4 to 40 carbon atoms (eg, triethylamine, ethyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, etc.), E of aliphatic amine (2-40 carbon atoms)
O (2 mol or more) adduct, alicyclic amine having 6 to 40 carbon atoms (for example, N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine and 1,8-diazabicyclo ( 5,4,0)-
7-undecene and the like; a nitrogen-containing heterocyclic aromatic amine having 5 to 30 carbon atoms (for example, 4-dimethylaminopyridine;
N-methylimidazole, 4,4'-dipyridyl and the like)
And inorganic or organic acid salts of tertiary amines such as triethanolamine monostearate and stearamidoethyldiethylmethylethanolamine.

As the amphoteric surfactant, a carboxylate type amphoteric surfactant, a sulfate ester type amphoteric surfactant, a sulfonate type amphoteric surfactant, a phosphate ester type amphoteric surfactant and the like can be used. .

As the carboxylate-type amphoteric surfactant, an amino acid-type amphoteric surfactant, a betaine-type amphoteric surfactant, an imidazoline-type amphoteric surfactant and the like are used. The amino acid type amphoteric surfactant is an amphoteric surfactant having an amino group and a carboxyl group in the molecule. Sodium, sodium laurylaminopropionate); alkyl (4 to 24 carbon atoms) aminoacetic acid-type amphoteric surfactant (such as sodium laurylaminoacetate).

The betaine-type amphoteric surfactant is an amphoteric surfactant having a quaternary ammonium salt-type cation portion and a carboxylic acid-type anion portion in the molecule, for example, an alkyl (having 6 to 40 carbon atoms). ) Dimethyl betaine (such as betaine stearyl dimethylaminoacetate and betaine lauryl dimethylaminoacetate), amide betaine having 6 to 40 carbon atoms (such as coconut oil fatty acid amide propyl betaine), alkyl (6 to 40 carbon atoms) dihydroxyalkyl (6 carbon atoms) To 40) betaine (lauryl dihydroxyethyl betaine and the like) and the like.

The imidazoline-type amphoteric surfactants include
It is an amphoteric surfactant having a cation moiety having an imidazoline ring and a carboxylic acid-type anion moiety, and examples thereof include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.

As other amphoteric surfactants, for example,
Glycine type amphoteric surfactants such as sodium lauroyl glycine, sodium lauryl diaminoethyl glycine, lauryl diaminoethyl glycine hydrochloride, dioctyl diaminoethyl glycine hydrochloride; sulfobetaine type amphoteric surfactants such as pentadecyl sulfotaurine, sulfonate type Examples include amphoteric surfactants and phosphate ester type amphoteric surfactants.

As the nonionic surfactant, an AO addition type nonionic surfactant, a polyhydric alcohol type nonionic surfactant and the like can be used. AO-added nonionic surfactants include higher alcohols having 8 to 40 carbon atoms, and higher alcohols having 8 to 4 carbon atoms.
AO (C2-20) is directly added to a higher fatty acid of 0 or an alkylamine having 8 to 40 carbon atoms, or a higher fatty acid or the like is added to a polyalkylene glycol obtained by adding AO to glycol. It is obtained by adding AO to an esterified product obtained by reacting a higher fatty acid with a polyhydric alcohol, or adding AO to a higher fatty acid amide.

AO includes, for example, EO, PO and butylene oxide. Preferred among these are EO and random or block adducts of EO and PO. The number of moles of AO added is 10 to 5
0 mol is preferable, and AO in which 50 to 100% by weight of the AO is EO is preferable.

Examples of the AO addition type nonionic surfactant include:
For example, polyoxyalkylene alkyl or alkenyl ether (oxyalkylene having 2 to 24 carbon atoms, alkyl or alkenyl having 8 to 40 carbon atoms) (for example, octyl alcohol EO 20 mol adduct, lauryl alcohol EO 20 mol adduct, stearyl alcohol EO 10 mol) Adduct, oleyl alcohol EO 5 mol adduct, lauryl alcohol EO 10 mol PO 20 mol block adduct, etc.); polyoxyalkylene higher fatty acid ester (oxyalkylene having 2 to 24 carbon atoms, higher fatty acid having 8 to 40 carbon atoms) (for example, Stearyl acid EO10
Polyoxyalkylenealkylphenyl ether (oxyalkylene having 2 to 24 carbon atoms, alkyl having 8 to 4 carbon atoms)
0) (for example, nonylphenol EO 4 mol adduct, nonylphenol EO 8 mol PO20 mol block adduct, octylphenol EO 10 mol adduct, dinonylphenol EO 20 mol adduct, etc.); polyoxyalkylene alkylamino ether (oxyalkylene having 2 carbon atoms) To 24, alkyl having 8 to 40 carbon atoms (e.g., laurylamine EO 10 mol adduct); polyoxyalkylenealkanolamide (alkylene having 2 to 2 carbon atoms)
4. Amide (acyl moiety) having 8 to 24 carbon atoms (e.g., EO 10 mol adduct of hydroxyethyl lauric amide, EO2 of hydroxypropyl oleic amide)
0 mol adduct, 10 mol adduct of EO of dihydroxyethyl lauric amide, etc.).

As the polyhydric alcohol type nonionic surfactant, polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid ester AO adducts, polyhydric alcohol alkyl ethers and polyhydric alcohol alkyl ether AO adducts can be used. . The polyvalent (divalent to octavalent or higher) alcohol has 3 to 24 carbon atoms, the fatty acid has 8 to 40 carbon atoms, and the AO has 2 to 24 carbon atoms.

As polyhydric alcohol fatty acid esters,
Examples include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitan dilaurate, sorbitandiolate, and sucrose monostearate.

Examples of the polyhydric alcohol fatty acid ester AO adduct include ethylene glycol monooleate E
O10 mol adduct, 20 mol of ethylene glycol monostearate EO, 20 mol of trimethylolpropane monostearate EO, 10 mol of PO, 10 mol random adduct,
Examples include sorbitan monolaurate EO 10 mol adduct, sorbitan monostearate EO 20 mol adduct, sorbitan distearate EO 20 mol adduct, and sorbitan dilaurate EO 12 mol PO 24 mol random adduct.

Examples of the polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glycoside and lauryl glycoside.

Examples of the polyhydric alcohol alkyl ether AO adduct include sorbitan monostearyl ether EO 10 mol adduct, methyl glycoside EO 20 mol PO 10 mol random adduct, lauryl glycoside EO
10 mol adducts and stearyl glycosides EO 20 mol PO 20 mol random adducts and the like.

Examples of the water-soluble polymer include cellulose derivatives (eg, methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose and saponified products thereof, cationized cellulose, etc.), gelatin, soluble starch, dextrin, and the like. Gum arabic, chitin, chitosan, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethylene imine, polyacrylamide, acrylic acid (salt) containing polymers (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, water of polyacrylic acid) Partially neutralized sodium oxide,
Sodium acrylate-acrylate copolymer), sodium hydroxide (partially) neutralized styrene-maleic anhydride copolymer, water-soluble polyurethane (a reaction product of polyethylene glycol or the like with polyisocyanate, etc.) and the like. Can be

Among the water-soluble polymers, cellulose derivatives, starch, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol and acrylic acid (salt)
Containing polymers are preferred. The Mw of these aqueous polymers
Is usually 500 to 2,000,000.

The dispersant (D) is used by previously adding it to an aqueous dispersion medium. (D) is added in an amount of usually 0.01 to 10 parts, preferably 0.1 to 10 parts, per 100 parts of the above-mentioned adjusting solution.
Department.

To sharpen the particle size distribution of the dispersion,
Preferably, the dispersion is performed in the presence of organic or inorganic fine particles. The organic or inorganic fine particles are used by previously dispersing them in an aqueous dispersion medium. Examples of the organic fine particles include (co) polymers of the vinyl monomers (1) to (10), and examples of the inorganic fine particles include calcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide, and aluminum hydroxide. The organic fine particles may have the same composition and the same molecular weight as (A).

The median diameter of the fine particles is usually 0.01 to 1
It may be appropriately selected according to the intended use of the resin fine particle composition. The median diameter is measured by a laser diffraction particle size distribution analyzer “LA-920” (manufactured by Horiba, Ltd.). The amount of the fine particles to be used is generally 0 to 100 parts, preferably 0.1 to 100 parts, per 100 parts of the preparation liquid.
It is.

The ratio of the dispersant (D) in the aqueous medium is as follows:
Usually, it is 0.1 to 10%, preferably 0.2 to 9%, particularly preferably 0.3 to 8%.
50%, preferably 0 to 30%, and the proportion of fine particles is usually 0 to 50%, preferably 0 to 40%.

The amount of the aqueous medium used is usually 50 to 2,000 parts, preferably 70 to 800 parts, per 100 parts of the adjusting liquid.
Department.

The temperature at the time of mixing and dispersing the adjusting solution and the aqueous medium is usually 0 to 150 ° C., preferably 20 to 98 ° C. It may be at normal pressure or under pressure. The mixing time varies depending on the equipment used, but is usually 0.1 sec to 1 sec.
0 minute, preferably 0.5 second to 8 minutes, particularly preferably 1 second to 5 minutes.

The apparatus used for mixing the adjusting liquid and the aqueous medium is not particularly limited, and those commercially available as emulsifiers and dispersers can be used. For example, a batch type emulsifier such as a homogenizer (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto Homomixer (manufactured by Tokushu Kika Kogyo), Ebara Milder (manufactured by Arihara Seisakusho), TK pipeline homomixer (Special Kika Co., Ltd.), Colloid Mill (Shinko Pantech Co., Ltd.), Slasher, Trigonal Wet Pulverizer (Mitsui Miike Kakoki Co., Ltd.), Capitron (Eurotec Co., Ltd.), Fine Flow Mill (Taikai Kiko Co., Ltd.) ), High-pressure emulsifier such as APM Gaurin (manufactured by Gaurin), microfluidizer (manufactured by Mizuho Industries), high pressure emulsifier such as APV Gaurin (manufactured by Gaurin), etc. Vibration emulsifier such as membrane emulsifier, Vibromixer (manufactured by Reika Kogyo), and ultrasonic emulsifier such as ultrasonic homogenizer (manufactured by Branson). And the like. The resin composition particles of the present invention containing a solvent can be obtained by dispersing and mixing the above-mentioned adjustment liquid and an aqueous medium to which an emulsifier or a dispersant is added by the above-mentioned apparatus. This dispersion may be performed by a batch process, or may be continuously performed while feeding the adjusting liquid and the aqueous medium by a pump or the like.

The obtained dispersion is desolvated to obtain resin composition particles. The solvent removal temperature is usually 0 to 150 ° C, preferably 5 to 120 ° C, particularly preferably 10 to 100 ° C, and the pressure is usually 0.1 to 98 kPa, preferably 0.1 to 98 kPa.
It is 2 to 90 kPa. The time is generally 1 minute to 72 hours, preferably 2 minutes to 48 hours. As the apparatus, a batch type desolvation apparatus, a continuous type, a thin film type desolvation apparatus, and the like in which an ordinary kolben is provided with a stirring device and a cooling and recovery device for a volatile solvent can be used.

Average particle size of resin composition particles (D50)
Is usually 0.1 to 500 μm, and the particle size distribution (volume average particle size)
Dv / number average particle diameter Dn) is usually 1.05 to 5.0.
Yes, if both are set appropriately according to the intended use
Good. In addition, D50, volume average particle diameter, and number average particle diameter are as follows:
Coulter counter [For example, product name: Multityza
-III (manufactured by Coulter)]. Resin group
The BET specific surface area of the product particles is determined from the viewpoint of powder fluidity.
0.5-5.0m ^Two/ G. Note that B
The ET specific surface area is measured using a specific surface area meter (for example, trade name: QUA).
NTASORB, manufactured by Yuasa Ionics)
Constant (Measurement gas: He / Kr = 99.9 / 0.1 vol)
%, Calibration gas: nitrogen).

The second invention uses a reactive group-containing prepolymer (a-1), which is a precursor of (A), instead of the resin (A) of the first invention, and mixes it with an aqueous medium to prepare an emulsion or an emulsion. When a dispersion is obtained, a curing reaction is carried out with a curing agent (a-2) in an aqueous medium to form a resin (A). The curing agent includes a stretching agent and a crosslinking agent for performing a stretching reaction or a crosslinking reaction of the prepolymer. In the second invention, it is possible to lower the viscosity of the adjustment liquid, which is advantageous for reducing the particle size of the particles during emulsification / dispersion and sharpening the particle size distribution. It has the characteristic that resin can be made into particles.

A reactive group-containing prepolymer (a-1),
Examples of the combination of the curing agent (a-2) include the following. : (A-1) is a compound (a-1-1) having a functional group capable of reacting with an active hydrogen compound, and (a-2) is a compound (a-2-1) of an active hydrogen group-containing compound. combination. : Compound (a-1) wherein (a-1) has an active hydrogen group
2), wherein (a-2) is a compound of the compound (a-2-2) capable of reacting with an active hydrogen group.

In the above, the compound (a-1-1) having a functional group capable of reacting with an active hydrogen compound includes a compound having an isocyanate group, a blocked isocyanate group, an epoxy group, an acid anhydride group and an acid halide group. And the like. Of these, compounds having an isocyanate group, a blocked isocyanate group and an epoxy group are preferred. 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 (a-2-1) include polyamines, polyols, polythiols and water which may be blocked by a removable compound. Preferred among these are polyamines, polyamines which may be blocked with a removable compound, polyols and water.

Examples of the polyamine which may be blocked with a compound capable of being eliminated include the same as the above-mentioned polyamine (i) and (i) ketones having 3 to 8 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl). Ketimine compounds, oxazoline compounds, etc. obtained from

As the polyol, the above-mentioned diol (e
And diol (e-1) alone or a small amount of tri- or higher valent polyol (e-2). Are preferred. Examples of the polythiol include those similar to the above-mentioned polythiol (j). 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.); mono- or di-alkanolamines (monoethanolamine, diethanolamine, etc.); Methanol, ethanol, isopropanol, butanol, phenol; monomercaptan (butyl mercaptan, lauryl mercaptan, etc.) and the like.

The prepolymer (a-1) described above.
Examples of the active hydrogen group (a-1-2) include an amino group, a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), a mercapto group, a carboxyl group, and an organic group blocked with a compound capable of leaving them. Is 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 by a compound from which an amino group can be eliminated 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).

Compounds that can react with active hydrogen groups (a-2-
Examples of 2) include polyisocyanate, polyepoxide, polycarboxylic acid, polyanhydride and polyacid halide. Preferred among these are polyisocyanates and polyepoxides.

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

Examples of the polyepoxide include those similar to the above-mentioned polyepoxide (k), and preferred is polyglycidyl ether.

As the polycarboxylic acid, the above-mentioned dicarboxylic acid (f-1) and tri- or higher polycarboxylic acid (f-
The same thing as 2) is mentioned, and the preferable thing is also the same.

Examples of the polycarboxylic anhydride include pyromellitic anhydride. As the polyacid halides, 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). Examples of the reaction terminator include monoisocyanates (lauryl isocyanate, phenyl isocyanate, etc.), monoepoxides (butyl glycidyl ether, etc.), monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking monoamines (ketimine compounds, etc.) And monools (methanol, ethanol, isopropanol, butanol, phenol, and monomercaptan (butyl mercaptan, lauryl mercaptan, etc.)).

The equivalent ratio of the reactive group in the reactive group-containing prepolymer (a-1) to the active hydrogen group in (a-2) is usually 1/2 to 2/1, preferably 1.5 / 1. 1-1 / 1.5,
More preferably, it is 1.2 / 1 to 1 / 1.2. When (a-2) is water, water is handled as a divalent active hydrogen compound.

Examples of the prepolymer (a-1) include prepolymers such as polyester, epoxy resin and polyurethane. Epoxy resins include addition condensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) with epichlorohydrin. Examples of the polyurethane include a polyadduct of the above polyol and the above polyisocyanate.

The method for incorporating a reactive group into a polyester, an epoxy resin, a polyurethane or the like is as follows: a method in which one of the components is used in excess to leave the functional group of the component at the terminal; And a method of reacting a compound containing a reactive group with a reactive 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 constituent components is diol (e-1).
And / or a trivalent or higher polyol and a dicarboxylic acid (f-
The ratio of 1) and / or trivalent or higher polycarboxylic acid (f-2) is usually 2/1 to 1 / (COOH) as the equivalent ratio [OH] / [COOH] of hydroxyl group [OH] and carboxyl group [COOH]. 05
/ 1, preferably 1.5 / 1 to 1.05 / 1, more preferably 1.3 / 1 to 1.1 / 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 the prepolymer obtained by the above method with a polyisocyanate, an isocyanate group-containing prepolymer is obtained, and by reacting a polyepoxide, an epoxy group-containing prepolymer is obtained. Examples of the polyisocyanate include those similar to the above-mentioned polyisocyanate (g), 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 prepolymer to obtain an isocyanate group-containing polyester prepolymer, the ratio of the polyisocyanate is the isocyanate group [NCO] As the equivalent ratio [NCO] / [OH] of the hydroxyl group [OH] of the hydroxyl group-containing polyester,
Usually 5/1 to 1/1, preferably 4/1 to 1.2 / 1,
More preferably, it is 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 15% by Mn of the prepolymer / the number of reactive groups.
It is 0 to 30,000, preferably 300 to 10,000. Mn of (a-1) is usually 500 to 15,000.
0, preferably 1,000 to 20,000, more preferably 2,000 to 10,000. Mw of (a-1) is 1,000 to 50,000, preferably 2,000.
00 to 40,000, more preferably 4,000 to 2
It is 0000.

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

The curing reaction time depends on the prepolymer (a-1)
Is selected depending on the combination of the structure of the reactive group and the curing agent (a-2).
Hours, preferably 2 to 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 a reaction of isocyanate, dibutyltin dilaurate and dioctyltin dilaurate are mentioned. In the case of an epoxy reaction, for example, triphenylphosphine, triphenylphosphite, imidazoles (2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole,
Heptadecylimidazole, 2-ethyl-4-methylimidazole, etc.), tertiary amines [2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, α- Methylbenzylmethylamine, 1,8-
Diazabicyclo (5,4,0) undecene-7].

Further, together with the prepolymer (a-1),
During the reaction of (a-1) and (a-2) in an aqueous medium,
A polymer that does not react with (a-1) and (a-2) [a so-called dead polymer] can be contained in the system. That is, a resin that has not undergone a curing reaction can be contained together with a resin that has undergone a curing reaction of the prepolymer (a-1) in an aqueous medium. The ratio of the cured resin and the non-cured resin is usually 100/0 to 1 /
99, preferably 99/1 to 5/95, more preferably 90/10 to 10/90, particularly preferably 80/20.
１５15/85.

In the present invention, when forming the resin composition particles, other known additives may be used depending on the use. Examples of additives include fillers (such as calcium carbonate), antistatic agents [such as sodium salts of polystyrene (molecular weight: 1,000 to 500,000) sulfonic acid], release agents (synthetic waxes such as polyethylene wax and polypropylene wax, carnauba wax and the like). Natural wax, etc.), charge control agents (metal salts of alkylsalicylic acid, etc.) and ultraviolet absorbers (hindered phenols, methoxyhydroquinones, etc.). The resin composition particles and the above-mentioned other additives may be mixed at the time of mixing the adjustment liquid and the aqueous medium, but after previously mixing (a-1) or (A) or its raw material and the additives, It is more preferable to mix the mixture with an aqueous medium.

The particles of the resin composition of the present invention may be a centrifugal separator,
It is obtained by solid-liquid separation using a spacra filter, filter press or the like, and drying the obtained powder.
The conditions for centrifugation are usually 10 to 10,000 G, preferably 50 to 5,000 G, and usually 1 to 60 minutes, preferably 2 to 45 minutes. In the case of a pressurized filter, 0.0
098 to 9.8 MPa, preferably 0.049 to 0.9
Filtration can be performed by applying a pressure of 8 MPa. As a method for drying the obtained powder, a known apparatus such as a fluidized-bed dryer, a reduced-pressure dryer, and a circulation dryer can be used. The drying temperature is usually from 0 to 150 ° C, preferably from 20 to 150 ° C.
The drying time is usually from 1 minute to 72 hours, preferably from 2 minutes to 48 hours. If necessary, the particles can be classified using an air classifier or the like to obtain a particle size distribution according to the application.

The resin composition particles of the present invention have good pigment dispersibility, good color sharpness and transparency of the obtained resin film, and excellent heat melting property and powder fluidity. It is useful for paints, hot-melt molding resins, spacers for the production of electronic components such as liquid crystals, standard particles for electronic measurement equipment, toner used for electrophotography, electrostatic recording, electrostatic printing, and other molding materials.

[0139]

The present invention will be further described with reference to the following examples.
The present invention is not limited to this.

Production Example 1 [Synthesis of high molecular weight polyester (A-1)] 542 parts of adduct of bisphenol A with 2 mol of EO, bisphenol A
192 parts of a PO2 molar adduct, 300 parts of isophthalic acid,
49 parts of terephthalic acid and 2 parts of dibutyltin oxide are polycondensed at 230 ° C. for 6 hours under normal pressure.
The reaction was carried out for 5 hours while dehydrating under a reduced pressure of 5 mmHg.
n7300, Mw28000, OHV13, AV1.6
Was obtained as a high molecular weight polyester (A-1).

Production Example 2 [Synthesis of low molecular weight polyester (A-2)] 378 parts of adduct of bisphenol A with 2 mol of EO, bisphenol A
402 parts of a PO2 molar adduct, 100 parts of isophthalic acid,
205 parts of terephthalic acid and 2 parts of dibutyltin oxide are added, polycondensed at 230 ° C. for 6 hours under normal pressure, and then reacted for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, Mn2800, Mw5100, OHV = 53, A
A low molecular weight polyester with V = 1.2 was obtained.

Production Example 3 [Synthesis of Isocyanate Group-Containing Prepolymer (x)] In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 358 parts of an adduct of 2 mol of EO of bisphenol A and 2 mol of PO of bisphenol A were added. 381 parts of adduct, isophthalic acid 20
0 parts, 127 parts of terephthalic acid and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours under normal pressure, and further reacted for 5 hours while dehydrating at a reduced pressure of 10 to 15 mmHg to obtain a polyester preform of OHV25 and AV0.9. A polymer was obtained. The mixture was further cooled to 80 ° C, and 364 parts of ethyl acetate and 98 parts of isophorone diisocyanate were added.
For 2 hours, Mw 12000, NCO content 1.2
A 9% isocyanate group-containing prepolymer (x) in ethyl acetate (solid content: 75%) was obtained.

Production Example 4 [Synthesis of ketimine compound (y)] 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 carry out a reaction with the ketimine compound (y). ) Got.

Example 1 [Synthesis of Resin Composition Particles (1)] (A-1) 30 parts, (A-2) 70 parts, cyanimble
-Acetic acid of KRO (phthalocyanine pigment: Sanyo Dye)
15 parts of ethyl dispersion (solid content 33%), pigment dispersant
(I) [Disper Ayk-170 (Big Chemie
Made in Japan: Organic acid salt of amino-modified polyester, acid value
44, amine value 32, Mw 4500, solid content concentration 30
%)] 2 parts planetary mixer PLM-V-15V
(Manufactured by Inoue Seisakusho). [Solid content concentration 90%] In addition, the ethyl acetate dispersion of cyanine blue KRO was prepared in advance.
High-pressure homogenizer [Gaulin type G-5 (APV)
600 kg / cm^TwoPre-crushing at pressure
What was done was used. Then, raise the internal temperature to 80 ° C
And mixed at 24 rpm and 72 rpm for 1 hour.
The mixture was cooled to 45 ° C. with stirring and dispersed for 6 hours.
After that, ethyl acetate 95 is continuously charged over 2 hours to solidify.
An adjustment liquid (1) of a resin and a pigment having a concentration of 50% was obtained. 200 parts of deionized water in a beaker, hydroxya
Patite 10% suspension (Super Thai manufactured by Nippon Chemical Industry Co., Ltd.)
G) 35 parts, sodium dodecylbenzenesulfonate
And 0.1 part of the solution was uniformly dissolved. Then adjust the temperature to 20 ° C
While stirring at 5000 rpm with a TK homomixer.
Then, 100 parts of the adjustment liquid (1) was charged and stirred for 10 minutes.
The mixture is then transferred to a Kolben equipped with a stir bar and thermometer.
Then, the temperature was raised to 50 ° C., and the solvent was removed under reduced pressure. Filtration
Thereafter, the cake was dispersed and washed in 450 parts of 5% hydrochloric acid, and filtered again.
Was. This operation is further performed once with 200 parts of 5% hydrochloric acid and 5%
Once with 200 parts of sodium fluoride and 250 parts of ion-exchanged water
After repeating three times, dry with a normal air dryer, classify the air, and
Equivalent particle diameter D50 is 20 μm, BET specific surface area is 3.8 m ^Two
/ G of [resin composition particles (1)].

Example 2 [Synthesis of Resin Composition Particles (2)] (A-1) 10 parts,
(A-2) 90 parts, 15 parts of a cyanine blue KRO (phthalocyanine pigment: Sanyo Dye) ethyl acetate dispersion (solid content: 33%), 2 parts of pigment dispersant (I), and 48 parts of ethyl acetate Lee mixer PLM-V-15V
(Manufactured by Inoue Seisakusho). [Solid content concentration: 64%] Thereafter, the internal temperature was raised to 80 ° C, mixed for 1 hour at a revolution of 24 rpm and a rotation of 72 rpm, cooled to 45 ° C with stirring, and dispersed for 6 hours. Was continuously charged over 2 hours to obtain a resin / pigment adjusting liquid (2) having a solid content of 50%. Except for using this adjustment liquid (2), the same operation as in Example 1 was carried out to obtain [Resin composition particles (2)] having an average particle diameter D50 of 20 μm and a BET specific surface area of 3.6 m ² / g. Obtained. In this case, water becomes the elongating agent.

Example 3 [Synthesis of Resin Composition Particles (3)] 100 parts of an ethyl acetate solution of (x), Cyanine Blue KRO (manufactured by Sanyo Dye) 5
Parts, 2 parts of pigment dispersant (I)
MV-15V (manufactured by Inoue Seisakusho). [Solid content concentration: 75%] Then, at an internal temperature of 20 ° C., the revolution is 24 rpm, and the rotation is 72 rpm.
After dispersion for 7 hours, 54 parts of ethyl acetate was continuously charged over 2 hours to obtain a prepolymer / pigment adjusted liquid (3) having a solid content of 50%. Except for using this adjustment liquid (3), the same operation as in Example 1 was performed, and the average particle diameter D50 was 21 μm and the BET specific surface area was 3.5 m ² /
g of [Resin Composition Particles (3)] was obtained. In this case, water becomes the elongating agent.

Example 4 [Synthesis of Resin Composition Particles (4)] (A-2) 100 parts of a cyanine blue KRO (phthalocyanine pigment: Sanyo Dye) 20 parts (20% concentration) of ethyl acetate dispersion, 2 parts of the pigment dispersant (I) was charged into a planetary mixer PLM-V-15V (manufactured by Inoue Seisakusho). [Solid content concentration: 86%] Then, the temperature was raised to an internal temperature of 80 ° C, mixed at an orbit of 24 rpm and a rotation of 72 rpm for 1 hour, cooled to 45 ° C with stirring, and dispersed for 7 hours, followed by ethyl acetate. 90 parts were continuously charged over 2 hours, and further 20 parts of the above-mentioned isocyanate group-containing prepolymer (x) in ethyl acetate solution,
Ethyl acetate (1.2 parts) and ketimine compound (y) (1.2 parts) were mixed to obtain a resin / pigment adjusting liquid (4) having a solid content of 50%. Except for using this adjustment liquid (4), the same operation as in Example 1 was performed, and the average particle diameter D50 was obtained.
Of 18 μm and a BET specific surface area of 3.9 m ² / g [resin composition particles (4)].

Comparative Example 1 [Synthesis of Resin Composition Particles (5)] 70 parts of (A-2), 5 parts of cyanine blue KRO (manufactured by Sanyo Dye) and 2 parts of pigment dispersant (I) were mixed with a Henschel mixer (Mitsui Mitsui) Kakoki Co., Ltd.
And then kneaded with a twin-screw kneader (PCM-30, manufactured by Ikegai Co., Ltd.). Then, after finely pulverizing using a supersonic jet pulverizer LabJet (manufactured by Nippon Pneumatic Industries, Ltd.), 77 parts of ethyl acetate was added, and the mixture was stirred at 35 ° C. for 3 hours. (5) was obtained. Except for using this adjustment liquid (5), the same operation as in Example 1 was performed, and the average particle diameter D50 was 20 μm, and the BET specific surface area was 4.0 m ^2.
/ G of [resin composition particles (5)].

Comparative Example 2 Synthesis of Resin Composition Particles (6) 70 parts of (A-2), 5 parts of cyanine blue KRO (manufactured by Sanyo Dye) and 2 parts of pigment dispersant (I) were mixed with a planetary mixer PLM- V-15V
(Manufactured by Inoue Seisakusho). [Solid content concentration: 98%] Thereafter, the internal temperature was raised to 150 ° C., and the mixture was mixed at a revolution of 24 rpm and a rotation of 72 rpm for 1 hour.
After cooling to 7 ° C. and dispersion for 7 hours.
4 parts were continuously press-fitted over 2 hours to obtain a resin / pigment adjusting liquid (6) having a solid content of 50%. Except for using this adjustment liquid (6), the same operation as in Example 1 was performed, and the average particle diameter D50 was 18 μm, and the BET specific surface area was 4.1 m ^2.
/ G of [resin composition particles (6)].

Comparative Example 3 Synthesis of Resin Composition Particles (7) 70 parts of (A-2), 5 parts of cyanine blue KRO (manufactured by Sanyo Dye), 2 parts of pigment dispersant (I) and 112 parts of ethyl acetate It was charged in a planetary mixer PLM-V-15V (manufactured by Inoue Seisakusho).
[Solid Content Concentration 40%] Thereafter, the internal temperature was raised to 75 ° C., and the mixture was mixed at a revolution of 24 rpm and a rotation speed of 72 rpm for 1 hour. % Of a resin and pigment preparation liquid (7). Except that this adjusting solution (7) was used, the same operation as in Example 1 was performed, and the average particle diameter D50 was 14 μm, and the BET specific surface area was 4.4 m ^2.
/ G of [resin composition particles (7)].

Comparative Example 4 70 parts of (A-2), 20 parts of an ethyl acetate dispersion of cyanine blue KRO (phthalocyanine pigment: Sanyo Dye) (20% concentration), and 2 parts of pigment dispersant (I) were planetary. It was charged in a mixer PLM-V-15V (manufactured by Inoue Seisakusho). [Solid content concentration: 83%] Then, the temperature was raised to an internal temperature of 75 ° C, mixed at an orbit of 24 rpm and a rotational speed of 72 rpm for 1 hour, cooled to 25 ° C with stirring, and dispersed for 7 hours. 3 parts were added to obtain a resin / pigment adjusting liquid (8) having a solid content of 80%. Except for using this adjustment liquid (8), the same operation as in Example 1 was performed, but the adjustment liquid became lumpy in the aqueous medium and no dispersion was obtained.

Physical property measurement 1 Pigment dispersibility: The average particle diameter (D50) of the pigment and the content of pigment aggregates (particle diameter of 1 μm or more) in the adjusting liquids (1) to (7) were measured by a laser diffraction particle size distribution analyzer. It was measured with "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 more pigment dispersibility,
The stability over time of the pigment dispersion state in the adjustment liquid is good.

Physical property measurement 2 Color sharpness of resin film: resin composition particles (1) to (7)
0.1 g was placed on a glass piece having a length of 5 cm and a width of 5 cm, and another glass was placed on the glass while heating on a hot plate, and then pressure was applied to form a resin film. The chromaticity index and haze of the resin film are measured using a color difference meter “NDH
-300A "(manufactured by Nippon Denshoku Industries Co., Ltd.). Table 2 shows the evaluation results. Chromaticness index (a *, b *)
The color is more vivid as the absolute value of each measured value is larger, and the haze is more transparent as the measured value is smaller.

[0154]

[Table 1]

[0155]

[Table 2]

[0156]

The method of the present invention has the following effects. 1. The dispersibility of the pigment dispersion is good and the dispersion state is excellent in stability over time. 2. The pigment dispersibility in the resin particles is good, and the resulting resin film is excellent in color sharpness and transparency. Because of the above effects, the resin composition particles obtained from the method of the present invention are powder coatings, 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 toner particles used for electrostatic recording, electrostatic printing, etc., various hot melt adhesives, and resin particles useful for molding materials and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/03 C09D 5/03 157/00 157/00 163/00 163/00 175/04 175/04 201 / 00 201/00 // B29K 101: 00 B29K 101: 00 C08L 101: 00 C08L 101: 00 (72) Inventor Tadakawa Tateo 11-11 Hitotsubashi Nohonmachi, Higashiyama-ku, Kyoto Sanyo Chemical Industry Co., Ltd. ) 4F070 AA01 AA46 AA47 AA53 AC43 AE04 AE14 AE28 FA05 FB06 FC02 4F201 AA03 AA13 AA24 AA31 AA39 AB03 AB12 BA02 BC01 BC12 BC33 BC37 BK01 BK15 BK38 BL03 BL43 4J034 CA02 CA03 CC04 CC03 CC03 CC03 CC65 CC67 CD01 CE01 DF01 DG03 DJ08 DK05 HA01 HA04 HA07 HA08 HB06 HB07 HC03 HC12 HC13 HC17 HC22 HC46 HC52 HC61 HC64 HC65 HC67 HC71 HC73 HD06 HD07 JA02 JA12 JA41 KB02 KC17 MA03 MA22 MA24 RA 07 4J036 AA01 AA02 AB01 AB03 AB06 AB07 AB08 AB09 AB12 AC01 AC02 AC03 AC06 AC13 AC19 AD08 AD09 AD21 AF01 AF06 AG04 AG05 AG07 AH01 AH05 AH07 AJ02 AJ17 AJ18 CD03 CD09 CD12 DB01 DB02 DB06 DB15 DB17 DB18 DB20 DC22 DC03 DC06 DC08 KA03 4J038 CA021 CB011 CB081 CB111 CC011 CC021 CC071 CD001 CF011 CG011 CG061 CG121 CG161 CG171 CG181 CH201 CK021 CM001 DB001 DB191 DD021 DD041 DG001 DK011 DM011 KA06 KA08 KA09 MA02 MA14

Claims (9)

[Claims] An aqueous dispersion is prepared by mixing a dispersion (I) in an organic solvent (C) containing a resin (A) and a pigment (B) with an aqueous medium containing a dispersant (D). In the method for producing resin composition particles by granulating, (I)
(B), (C) and, if necessary, a pigment dispersant (E) are mixed and dispersed by a mixer having a rotation and revolution function, and a mixed dispersion having a solid content of 50 to 98% by weight is diluted with an organic solvent as necessary. A method for producing resin composition particles, characterized in that it is an adjusted liquid having a solid content concentration of 20 to 70%. 2. An aqueous dispersion is prepared by mixing a dispersion (I) in an organic solvent (C) containing a resin (A) and a pigment (B) with an aqueous medium containing a dispersant (D). In the method for producing resin composition particles by granulation, (I) is a reactive group-containing prepolymer (a-1) which is a precursor of (A);
(B), (C) and, if necessary, a pigment dispersant (E) are mixed and dispersed by a mixer having a rotation and revolution function, and a mixed dispersion having a solid content of 50 to 98% by weight is diluted with an organic solvent, if necessary. It is an adjustment liquid having a solid concentration of 20 to 70%,
A method for producing resin composition particles, characterized in that when mixing (I) and an aqueous medium, (a-1) is cured with a curing agent (a-2) to form a resin (A). 3. 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,
The production method according to claim 2, wherein (a-2) is a compound (a-2-1) having an active hydrogen atom-containing group which may be blocked. 4. The method according to claim 3, wherein (a-2-1) is water or a ketimine compound. 5. The production method according to claim 1, wherein the mixer having a rotation and revolution function is a planetary mixer or a universal mixer. 6. The resin (A) is at least one resin selected from the group consisting of vinyl resins, polyester resins, polyurethane resins and epoxy resins.
The production method according to any one of the above. 7. A pigment (B) having a white color, a blue color, a red color,
The method according to any one of claims 1 to 6, comprising a yellow and / or black pigment. 8. The manufacturing method according to claim 1,
And the average particle diameter (D50) is 0.1 to 500 μm
And the BET specific surface area is 0.5 to 5.0 m ^Two/ G
Resin composition particles. 9. A powder coating comprising the resin composition particles obtained by the production method according to claim 1.