JP3455523B2 - Resin particles having a uniform particle size and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin dispersion having a uniform particle size, resin particles and a method for producing them. More specifically, resin for slush molding, powder coating, spacers for manufacturing electronic parts such as liquid crystal displays, standard particles for electronic measuring instruments, toner used for electronic photography, electrostatic recording, electrostatic printing, hot melt adhesives. ,
The present invention also relates to resin particles useful for molding materials and the like, an aqueous resin dispersion thereof, and a method for producing them.

[0002]

2. Description of the Related Art Conventionally, a resin solution prepared by dissolving a resin in a solvent in advance is dispersed in an aqueous medium in the presence of a dispersing agent such as a surfactant or a water-soluble polymer, and this is heated or reduced in pressure. A method of removing resin to obtain resin particles (dissolved resin suspension method) is known (Japanese Patent Publication No. 61-
28688, JP-A-63-25664, etc.)
However, there is a drawback in that the uniformity of the particle size of the obtained particles is insufficient, and a classification step is required to make the particle size uniform. Further, in the dissolved resin suspension method, a method for obtaining resin particles having a uniform particle size by using an inorganic fine powder such as calcium carbonate or silica as a dispersion stabilizer (JP-A-9-31).
No. 9144). However, the inorganic fine powder is attached to the resin particles obtained by these methods. The inorganic powder is difficult to remove,
Even if the removal step is provided, there is a drawback that a small amount of the remaining inorganic powder impairs the electrical characteristics, thermal characteristics, chemical stability and the like of the resin particles.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances in the prior art. That is, it is an object to provide a resin dispersion having a uniform particle diameter, a method for producing resin particles, and the like.

[0004]

The present invention has been made in view of the above circumstances in the prior art. That is, it is an object to provide resin particles having a uniform particle diameter, a method for producing the same, and the like. That is, the present invention is to disperse a resin (b) or a solvent solution thereof, or a precursor (b0) of the resin (b) or a solvent solution thereof in an aqueous dispersion liquid of resin particles (A) composed of a resin (a). When the precursor (b0) or its solvent solution is used,
By reacting the precursor (b0) to form resin particles (B) composed of the resin (b) in the aqueous dispersion liquid of the resin particles (A), the resin particles (B) are formed on the surface of the resin particles (B). A method for producing resin particles, which comprises forming an aqueous dispersion (X1) of resin particles (C) having a structure in which A) is attached and removing the aqueous medium from the (X1). Furthermore, the present invention is also a resin particle obtained by the above production method. Furthermore, the present invention provides resin particles (C) having a structure in which resin particles (A) made of resin (a) are attached to the surface of resin particles (B) made of resin (b), wherein: The ratio of the volume average particle diameter of the particles (A) to the resin particles (B) is 0.001 to 0.3, and the volume average particle diameter of the resin particles (A) is 0.01 to 30.
and the volume average particle size of the resin particles (B) is 0.1 to 300 μm, and the value of the volume average particle size / number average particle size of the resin particles (C) is 1.00 to 1.20. And: 5% or more of the surface of the resin particles (B) is the resin particles (A)
The BET value specific surface area of the resin particles (C) is 0.5 to 5.
0 m ² / g, and the surface average center line roughness Ra of the resin particles (C) is 0.0.
1 to 0.8 μm, and: Wadell's practical sphericity of the resin particles (C) is 0.
90 to 1.00, and: Resin particles, wherein the resin (a) and / or the resin (b) is at least one resin selected from the group consisting of polyurethane resin, epoxy resin, vinyl resin and polyester resin. And resin particles comprising the resin (b), wherein the value of volume average particle diameter / number average particle diameter of resin particles is 1.00 to 1.20, and: BET value specific surface area of resin particles Is 0.5 to 5.0 m ²
/ G: The surface average centerline roughness Ra of the resin particles is 0.01 to
0.8 μm: Practical sphericity of resin particles of Wadell is 0.90
It is also 1.00, and is also a resin particle in which the resin (b) is at least one resin selected from the group consisting of polyurethane resin, epoxy resin, vinyl resin and polyester resin. The present invention is described in detail below.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as the resin (a), any resin can be used as long as it is a resin capable of forming an aqueous dispersion, and it may be a thermoplastic resin or a thermosetting resin. There may be, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like. To be
As the resin (a), two or more kinds of the above resins may be used in combination. Among these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferable from the viewpoint of easily obtaining an aqueous dispersion of fine spherical resin particles.

The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of vinyl-based monomers include the following (1) to (10).

(1) Vinyl-based hydrocarbons: (1-1) Aliphatic vinyl-based hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other than the above. Α-olefins, etc .; alkadienes such as butadiene, isoprene, 1,4-
Pentadiene, 1,6-hexadiene, 1,7-octadiene. (1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidene bicycloheptene; terpenes,
For example, pinene, limonene, indene, etc. (1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products such as α-
Methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene and the like; and Vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomer and salt thereof: 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, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester Carboxyl group-containing vinyl monomers such as cinnamic acid.

(3) Sulfone group-containing vinyl type monomer, vinyl type sulfuric acid monoester and salts thereof: carbon number 2
To 14 alkene sulfonic acids, such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; and C 2-24 alkyl derivatives thereof, such as α-methyl styrene sulfonic acid; sulfo ( Hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, for example sulfopropyl (meth) acrylate, 2-hydroxy-3-
(Meth) acryloxypropyl sulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropane sulfone Acid, 2- (meth) acrylamide-
2-methylpropanesulfonic acid, 3- (meth) acrylamido-2-hydroxypropanesulfonic acid, alkyl (C3-18) allylsulfosuccinic acid, poly (n =
2 to 30) oxyalkylene (ethylene, propylene,
Butylene: single, random, or block) sulfuric acid ester of mono (meth) acrylate [poly (n = 5 to 5
15) Oxypropylene monomethacrylate sulfate ester, etc.], polyoxyethylene polycyclic phenyl ether sulfate ester, and sulfate ester or sulfonic acid group-containing monomer represented by the following general formulas (3-1) to (3-3); Salt etc. (In the formula, R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different, and when different, they may be random or block. Ar represents a benzene ring, n represents an integer of 1 to 50, and R'represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom.)

(4) Phosphoric acid group-containing vinyl monomer and its salt: (meth) acryloyloxyalkyl (C1-C2
4) Phosphoric acid monoester, for example, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (having 1 to 24 carbon atoms) phosphonic acids,
For example, 2-acryloyloxyethylphosphonic acid

Examples of the salts (2) to (4) include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (calcium salt, magnesium salt, etc.),
Examples thereof include ammonium salt, amine salt and quaternary ammonium salt.

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

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

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

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

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

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

Examples of the vinyl-based monomer copolymer include polymers obtained by copolymerizing the above-mentioned arbitrary monomers (1) to (10) with each other in a binary or more number in an arbitrary ratio. For example, styrene- (meth) acrylic acid ester copolymer, styrene-butadiene copolymer, (meth)
Acrylic acid-acrylic acid ester copolymer, styrene-
Acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid, divinylbenzene copolymer, styrene-styrenesulfonic acid- (meth) acrylic acid Examples thereof include ester copolymers.

Since it is necessary to form the resin particles (A) in the aqueous dispersion, the resin (a) is not completely dissolved in water under at least the conditions for forming the aqueous dispersion (X1). It is necessary. Therefore, when the vinyl-based resin is a copolymer, the ratio of the hydrophobic monomer and the hydrophilic monomer constituting the vinyl-based resin depends on the kind of the selected monomer, but the hydrophobic monomer is generally 10% or more. It is preferable that it is 30% or more. When the ratio of the hydrophobic monomer is 10% or less, the vinyl resin becomes water-soluble and the particle size uniformity of (C) is impaired. Here, the hydrophilic monomer refers to a monomer that dissolves in water at an arbitrary ratio, and the hydrophobic monomer refers to other monomers (basically immiscible with water).
Say.

Examples of the polyester resin include polycondensates of polyol and polycarboxylic acid or its acid anhydride or its lower alkyl ester. The polyol is a diol (11) and a trivalent or higher valent polyol (12), and the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (13) and a trivalent or higher valent polycarboxylic acid (14). And their acid anhydrides or lower alkyl esters. The ratio of the polyol to the polycarboxylic acid is the equivalent ratio [OH] / of the hydroxyl group [OH] and the carboxyl group [COOH] /
[COOH] is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.3 / 1 to
It is 1.02 / 1.

Examples of the diol (11) include alkylene glycols (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, Dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc .; alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol) ); Alicyclic diol (1,
4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxides of the above alicyclic diols (ethylene oxide, propylene oxide, butylene oxide, etc.)
Additives; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols; and polylactone diol (poly ε-caprolactone diol, etc.), polybutadiene diol, etc. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycol having 2 to 12 carbon atoms. It is a combination of. Examples of the trihydric or higher polyol (12) include polyhydric aliphatic alcohols having a valency of 3 to 8 or higher (glycerin, trimethylolethane,
Trimethylolpropane, pentaerythritol, sorbitol, etc.); trisphenols (Trisphenol PA, etc.); novolac resins (phenol novolac, cresol novolac, etc.); alkylene oxide adducts of the above trisphenols; alkylene oxide adducts of the above novolak resins And so on. Acrylic polyol [Hydroxyethyl (meth) acrylate and other vinyl-based copolymers, etc.] Of these, preferred are polyhydric aliphatic alcohols having 3 to 8 valences or more and alkylene oxide adducts of novolac resins. And particularly preferred is an alkylene oxide adduct of novolac resin.

Examples of the dicarboxylic acid (13) include alkylenedicarboxylic acids (succinic acid, adipic acid, sebacic acid,
Dodecenylsuccinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, etc.);
Alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); C8 or more branched alkylene dicarboxylic acid [dimer acid, alkenyl succinic acid (dodecenyl succinic acid,
Pentadecenyl succinic acid, octadecenyl succinic acid, etc.), alkyl succinic acid (decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid) Etc.) and the like. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). As the dicarboxylic acid (13) or the tricarboxylic or higher polycarboxylic acid (14), an acid anhydride or a lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above may be used.

As the polyurethane resin, polyisocyanate (15) and active hydrogen group-containing compound (D) {water, polyol [the aforementioned diol (11) and trivalent or higher valent polyol (12)], dicarboxylic acid (13), 3 Polycarboxylic acid (14) having a valency or more, polyamine (16), polythiol (17), and the like} and polyaddition products thereof can be mentioned.

As the polyisocyanate (15), aromatic polyisocyanate having 6 to 20 carbon atoms (excluding carbon in NCO group, the same applies hereinafter), aliphatic polyisocyanate having 2 to 18 carbon atoms, and 4 to 15 carbon atoms. Alicyclic polyisocyanates, araliphatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanate) Nulate groups, oxazolidone group-containing modified products, etc.) and mixtures of two or more thereof.
Specific examples of the aromatic polyisocyanate include 1,
3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or
Or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane with a small amount (for example, 5 to 20% by weight)] Mixture with trifunctional or higher functional polyamine]: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- and p-isocyanate Natophenyl sulfonyl isocyanate, etc. Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate. 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6
-Diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,
Examples thereof include aliphatic polyisocyanates such as 6-diisocyanatohexanoate. Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI) and 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 and the like can be mentioned. Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′,
α'-Tetramethylxylylene diisocyanate (TM
XDI) and the like. Examples of the modified polyisocyanate include urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group-containing modified product. In particular,
Modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and other modified polyisocyanates and mixtures of two or more thereof [for example, modified MDI and urethane-modified TDI (isocyanate-containing prepolymers ) Combined use]. Of these, preferred are 6 to 15 aromatic polyisocyanates, C4 to C12 aliphatic polyisocyanates, and C4 to C15 alicyclic polyisocyanates, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

Examples of the polyamine (16) include aliphatic polyamines (C2 to C18): aliphatic polyamine {C
2-C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylene Tetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]};
These alkyl (C1 to C4) or hydroxyalkyl (C2 to C4) substituted products [dialkyl (C1 to C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexa Methylenediamine, methyliminobispropylamine, etc.]; Aliphatic or heterocyclic aliphatic polyamine [3,9-bis (3-aminopropyl)-
2,4,8,10-Tetraoxaspiro [5,5] undecane, etc.]; Aromatic ring-containing aliphatic amines (C8-C
15) (Xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamine (C4 to C1
5): 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.,
Heterocyclic polyamines (C4 to C15): piperazine, N-
Aromatic polyamines such as aminoethylpiperazine, 1,4-diaminoethylpiperazine and 1,4bis (2-amino-2-methylpropyl) piperazine (C6 to C2
0): unsubstituted aromatic polyamine [1,2-, 1,3-
And 1,4-phenylenediamine, 2,4'- and 4,4'-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) Sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ', 4 "-triamine, naphthylenediamine, etc .; nuclear-substituted alkyl groups [methyl, ethyl, n- and i-propyl, An aromatic polyamine having a C1 to C4 alkyl group such as butyl) such as 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'-diaminodiphenyl sulfone, 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-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5- Nitro-1,3-
Phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,
5'-dibromo-diphenylmethane, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4 -Amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4'-methylenebis (2-bromoaniline), 4,4'-methylenebis (2-fluoroaniline) , 4-aminophenyl-2-chloroaniline, etc.]; Aromatic polyamines having a secondary amino group Down [some or all of -NH ₂ of the aromatic polyamines of the ~ is -NH-R'(R'is an alkyl group such as methyl, lower alkyl group such as ethyl) those were Tsu replace with] [4,
4'-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.], polyamide polyamine: dicarboxylic acid (dimer acid, etc.)
Polyamines such as low molecular weight polyamide polyamines obtained by condensation of polyamines with excess polyamines (2 moles or more per 1 mole of acid) (the above-mentioned alkylenediamines, polyalkylenepolyamines, etc.), polyetherpolyamines: polyetherpolyols (polyalkyleneglycols, etc.) And hydrides of cyanoethylated compounds.

Examples of the polythiol (17) include ethylenedithiol, 1,4-butanedithiol and 1,6-hexanedithiol.

As the epoxy resin, a ring-opening polymer of a polyepoxide (18), a polyepoxide (18) and an active hydrogen group-containing compound (D) {water, polyol [the above-mentioned diol (11) and trivalent or higher valent polyol (12)] ], Dicarboxylic acid (13), trivalent or higher polycarboxylic acid (1
4), polyamine (16), polythiol (17), etc.}
Or a polyaddition product of polyepoxide (18) with a dicarboxylic acid (13) or a polycarboxylic acid having a valence of 3 or more (1
A cured product of the acid anhydride of 4) and the like can be mentioned.

The polyepoxide (18) of the present invention is not particularly limited as long as it has two or more epoxy groups in the molecule. The polyepoxide (18) is preferably one having 2 to 6 epoxy groups in the molecule from the viewpoint of mechanical properties of the cured product. Polyepoxide (18)
The epoxy equivalent (molecular weight per epoxy group) of is
It is usually 65 to 1000, preferably 90 to 500
Is. If the epoxy equivalent exceeds 1,000, the crosslinked structure becomes loose and the physical properties of the cured product such as water resistance, chemical resistance and mechanical strength deteriorate, while it is difficult to synthesize those with an epoxy equivalent of less than 65. is there.

Examples of the polyepoxide (18) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds and aliphatic polyepoxy compounds. Examples of aromatic polyepoxy compounds include glycidyl ethers and glycidyl esters of polyhydric phenols, glycidyl aromatic polyamines, and glycidyl compounds of aminophenols. Examples of the glycidyl ether of polyhydric phenol 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, tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4 ′
-Dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethane tetraglycidyl ether, p-glycidyl phenyl dimethyltolyl bisphenol A glycidyl ether, trismethyl-tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furo orange glycidyl ether, 4,4'-oxybis (1 , 4-Phenylethyl) tetracresol glycidyl ether, 4,4′-oxybis (1,4-
Phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, glycidyl ether of phenol or cresol novolac resin, glycidyl ether of limonenephenol novolac resin, obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin Examples thereof include a polyglycidyl ether body of polyphenol obtained by a condensation reaction of phenol and glyoxal, glutaraldehyde, or formaldehyde, and a polyglycidyl ether body of a polyphenol obtained by a condensation reaction of resorcin and acetone. Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate. Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′,
N'-tetraglycidyl xylylenediamine, N, N,
N ', N'- tetraglycidyl diphenyl methanediamine etc. are mentioned. Furthermore, in the present invention, as the aromatic system, a triglycidyl ether of P-aminophenol, a diglycidyl urethane compound obtained by an addition reaction of tolylene diisocyanate or diphenylmethane diisocyanate and glycidol, and a polyol obtained by reacting the two reaction products with a polyol are also obtained. Also included are glycidyl group-containing polyurethane (pre) polymers and diglycidyl ethers of alkylene oxide (ethylene oxide or propylene oxide) adducts of bisphenol A. Examples of the heterocyclic polyepoxy compound include trisglycidyl melamine; examples of the alicyclic polyepoxy compound include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, and bis (2,3-epoxycyclopentyl). Ether, ethylene glycol bisepoxy dicyclopentyl ale,
3,4-epoxy-6-methylcyclohexylmethyl-
3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,3
4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester and the like can be mentioned. The alicyclic compounds also include nuclear hydrogenated products of the above aromatic polyepoxide compounds; the aliphatic polyepoxy compounds include polyglycidyl ethers of polyhydric aliphatic alcohols and polyglycidyl esters of polyhydric fatty acids. Body, and glycidyl fatty amines. Examples of the polyglycidyl ether of polyhydric aliphatic alcohol include 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, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerolin polyglycidyl ether, etc. Can be mentioned. Examples of polyglycidyl ester of polyhydric fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. In addition, in the present invention, the aliphatic system also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. The polyepoxide of the present invention may be used in combination of two or more kinds.

In the present invention, the resin (b) or its solvent solution or the resin (b) precursor (b0) or its solvent solution is added to the aqueous dispersion of the resin particles (A) comprising the resin (a). By dispersing and reacting the precursor (b0) if necessary, and adsorbing the resin particles (A) on the surface of the resin particles (B) when the resin particles (B) are formed,
It prevents the resin particles (B) or the resin particles (C) from coalescing with each other, and makes the resin particles (C) less likely to be split under high shear conditions. Thereby, the particle diameter of the resin particles (C) is converged to a constant value, and the effect of enhancing the uniformity of particle diameter is exhibited. Therefore, the resin particles (A) have such a strength that they are not destroyed by shearing at the temperature at which they are dispersed, are difficult to dissolve in water or swell, and the resin (b) or its solvent solution or resin. It is preferable that the precursor (b0) of (b) or its solvent solution is less likely to be dissolved or swelled.

The glass transition temperature (Tg) of the resin (a) is
From the viewpoint of particle size uniformity of the resin particles (C), powder fluidity, heat resistance during storage, and stress resistance, usually 0 ° C to 300 ° C,
Preferably 20 ° C to 250 ° C, more preferably 50 ° C to
It is 200 ° C. When the Tg is lower than the temperature at which the aqueous dispersion (X1) is prepared, the effect of preventing coalescence and the prevention of splitting becomes small, and the effect of enhancing the uniformity of particle diameter becomes small. The Tg in the present invention is a value obtained from DSC measurement.

In Shore D hardness which is a standard of hardness,
The hardness of the resin particles (A) is usually 30 or more, particularly 45 to 10
It is preferably in the range of 0. Further, the hardness when immersed in a solvent in water for a certain period of time is preferably within the above range.

From the viewpoint of reducing the solubility or swelling of the resin particles (A) in water or the solvent used for dispersion, the molecular weight and SP value (of the SP value) of the resin (a) are reduced. The calculation method is Polymer Engineering
and Science, February, 19
74, Vol. 14, No. 2 P. 147 to 154), crystallinity, molecular weight between cross-linking points and the like are preferably adjusted appropriately.

The number average molecular weight (measured by GPC, hereinafter abbreviated as Mn) of the resin (a) is usually 2 to 5,000,000, preferably 2,000 to 500,000, and the SP value is usually 7
-18, preferably 8-14. The melting point of the resin (a) (measured by DSC) is usually 50 ° C. or higher, preferably 8
It is 0 ° C or higher. Further, in order to improve the heat resistance, water resistance, chemical resistance, particle size uniformity, etc. of the resin particles (C), a crosslinked structure may be introduced into the resin (a). Such a crosslinked structure has a covalent bond, a coordinate bond, an ionic bond,
Any cross-linking form such as hydrogen bondability may be used. When introducing a crosslinked structure into the resin (a), the molecular weight between crosslinking points is
It is usually 30 or more, preferably 50 or more. On the other hand, when it is desired to dissolve the resin particles (A) from the resin particles (C) to form the aqueous dispersion (X2) of the resin particles (B), it is preferable not to introduce a crosslinked structure.

The method for converting the resin (a) into an aqueous dispersion of the resin particles (A) is not particularly limited, but the following are listed. In the case of a vinyl resin, a method of directly producing an aqueous dispersion of resin particles (A) by using a monomer as a starting material and performing a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method. In the case of polyaddition or condensation resins such as polyester resin, polyurethane resin and epoxy resin, the precursor (monomer, oligomer etc.) or its solvent solution is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated. Or a method of producing an aqueous dispersion of resin particles (A) by curing by adding a curing agent, or in the case of a polyaddition or condensation resin such as polyester resin, polyurethane resin or epoxy resin, a precursor (monomer) , Oligomer, etc.) or a solvent solution thereof (preferably a liquid, which may be liquefied by heating).
Method in which a suitable emulsifier is dissolved in water, and then water is added to perform phase inversion emulsification.
The resin prepared by any polymerization reaction method such as addition condensation, condensation polymerization, etc.) may be pulverized by using a fine pulverizer such as a mechanical rotary type or a jet type, and then the resin particles may be separated by sizing. After obtaining, a method of dispersing in water in the presence of a suitable dispersant Polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition,
Any polymerization reaction method such as addition condensation or condensation polymerization may be used) to obtain resin particles by spraying a resin solution prepared by dissolving a resin prepared in a solvent into a mist, and then dispersing the resin particles appropriately. Method of dispersing in water in the presence of agent In advance polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition,
By adding a poor solvent to a resin solution prepared by dissolving a resin prepared by addition condensation, condensation polymerization, or any other polymerization reaction method) in a solvent, or by cooling a resin solution prepared by heating in a solvent in advance. A method of precipitating resin particles, then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of an appropriate dispersant. Polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition,
The resin solution prepared by dissolving the resin prepared by addition condensation, condensation polymerization or any other polymerization reaction method) in a solvent is dispersed in an aqueous medium in the presence of an appropriate dispersant, and heated or decompressed. Method of removing solvent by polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition,
(Any type of polymerization reaction such as addition condensation, condensation polymerization, etc. may be used)) A method in which a suitable emulsifier is dissolved in a resin solution prepared by dissolving a resin in a solvent, and then water is added to carry out phase inversion emulsification.

In the above methods (1) to (3), as the emulsifier or dispersant used in combination, a known surfactant (S), water-soluble polymer (T) or the like can be used. Further, a solvent (U), a plasticizer (V) and the like can be used together as an emulsifying or dispersing aid.

As the surfactant (S), anionic surfactant (S-1), cationic surfactant (S-2), amphoteric surfactant (S-3), nonionic surfactant (S-).
4) etc. are mentioned. The surfactant (S) may be a combination of two or more kinds of surfactants.

As the anionic surfactant (S-1),
Examples thereof include carboxylic acid or its salt, sulfate ester salt, carboxymethylated salt, sulfonate salt and phosphate ester salt.

Examples of the carboxylic acid or its salt include saturated or unsaturated fatty acids having 8 to 22 carbon atoms or salts thereof, and specifically, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid. , Behenic acid, oleic acid, linoleic acid, ricinoleic acid and mixtures of higher fatty acids obtained by saponifying coconut oil, palm kernel oil, rice bran oil, beef tallow, and the like. Examples of the salt include salts of sodium, potassium, ammonium, alkanolamine and the like.

As the sulfuric acid ester salt, higher alcohol sulfuric acid ester salt (sulfuric acid ester salt of aliphatic alcohol having 8 to 18 carbon atoms), higher alkyl ether sulfuric acid ester salt (ethylene oxide 1 of aliphatic alcohol having 8 to 18 carbon atoms) -10 mol adduct sulfate ester salt), sulfated oil (natural unsaturated fat or oil or unsaturated wax directly sulfated and neutralized), sulfated fatty acid ester (lower alcohol ester of unsaturated fatty acid is sulfated) And neutralized) and a sulfated olefin (an olefin having 12 to 18 carbon atoms that is sulfated and neutralized). Examples of the salt include sodium salt, potassium salt, ammonium salt, and alkanolamine salt. Specific examples of the higher alcohol sulfate ester salt include octyl alcohol sulfate ester salt, decyl alcohol sulfate ester salt,
Lauryl alcohol sulfate ester, stearyl alcohol sulfate ester, alcohol synthesized using Ziegler catalyst (for example, ALFOL 1214: CON
Sulfate ester salt of DEA Co., alcohol synthesized by oxo method (for example, Dovanol 23, 25, 45: Mitsubishi Yuka, Tridecanol: Kyowa Hakko, Oxochol 1213, 1215, 1415: Nissan Kagaku, Diadol 115 -L, 115H, 135: manufactured by Mitsubishi Kasei); specific examples of higher alkyl ether sulfuric acid ester salts include lauryl alcohol ethylene oxide 2 mol adduct sulfuric acid ester salt and octyl alcohol ethylene oxide 3 mol adduct sulfuric acid ester. Salts: Specific examples of sulfated oils include sodium, potassium, ammonium, alkanolamine salts and sulfated fatty acid esters of sulfated compounds such as castor oil, peanut oil, olive oil, rapeseed oil, beef tallow, and sheep fat. Butyl oleate, ricinoleic acid Sodium sulfates such as Le, potassium, ammonium, alkanolamine salts;
As a specific example of the sulfated olefin, Tiepol (manufactured by Shell Co.) can be mentioned.

Examples of the carboxymethylated salt include salts of a carboxymethylated product of an aliphatic alcohol having 8 to 16 carbon atoms and carboxymethylated products of 1 to 10 mol of ethylene oxide adduct of an aliphatic alcohol having 8 to 16 carbon atoms. Examples include salt. Specific examples of salts of carboxymethylated aliphatic alcohols include octyl alcohol carboxymethylated sodium salt, decyl alcohol carboxymethylated sodium salt, lauryl alcohol carboxymethylated sodium salt, dovanol 23 carboxymethylated sodium salt, tridecanol. Carboxymethylated sodium salt ,; Specific examples of the salt of carboxymethylated product of ethylene oxide 1-10 mol adduct of aliphatic alcohol, octyl alcohol ethylene oxide 3 mol adduct carboxymethylated sodium salt,
Examples include lauryl alcohol ethylene oxide 4 mol adduct carboxymethylated sodium salt, dovanol 23 ethylene oxide 3 mol adduct carboxymethylated sodium salt, tridecanol ethylene oxide 5 mol adduct carboxymethylated sodium salt, and the like.

As the sulfonate, (d1) alkylbenzene sulfonate, (d2) alkylnaphthalene sulfonate, (d3) sulfosuccinic acid diester type,
Examples include (d4) α-olefin sulfonate, (d5) igepon T type, and (d6) sulfonate of other aromatic ring-containing compound. Specific examples of the alkylbenzene sulfonate include sodium dodecylbenzene sulfonate; specific examples of the alkylnaphthalene sulfonate include sodium dodecylnaphthalene sulfonate; specific examples of the sulfosuccinic acid diester type include sulfosuccinic acid di-2. -Ethylhexyl ester sodium salt and the like. Examples of the sulfonate of the aromatic ring-containing compound include mono- or disulfonate of alkylated diphenyl ether, styrenated phenolsulfonate, and the like.

Examples of the phosphoric acid ester salt include (e1) higher alcohol phosphoric acid ester salt and (e2) higher alcohol ethylene oxide adduct phosphoric acid ester salt.

Specific examples of the higher alcohol phosphoric acid ester salt include lauryl alcohol phosphoric acid monoester disodium salt, lauryl alcohol phosphoric acid diester sodium salt; and specific examples of the higher alcohol ethylene oxide adduct phosphoric acid ester salt include oleyl. Alcohol ethylene oxide 5 mol adduct phosphoric acid monoester disodium salt may be mentioned.

As the cationic surfactant (S-2),
Examples thereof include quaternary ammonium salt type and amine salt type.

As the quaternary ammonium salt type, a tertiary amine is reacted with a quaternizing agent (alkylating agent such as methyl chloride, methyl bromide, ethyl chloride, benzyl chloride and dimethylsulfate; ethylene oxide etc.). Obtained, for example, lauryl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, stearyl trimethyl ammonium bromide, lauryl dimethyl benzyl ammonium chloride (benzalkonium chloride), cetyl pyridinium chloride, polyoxyethylene trimethyl ammonium chloride, Examples include aramidethyldiethylmethylammonium methosulfate.

As the amine salt type, primary to tertiary amines are used as inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipic acid, alkyls). It is obtained by neutralizing with phosphoric acid or the like. For example, as the primary amine salt type, inorganic or organic acid salts of aliphatic higher amines (higher amines such as lauryl amine, stearyl amine, cetyl amine, hardened tallow amine, rosin amine); higher amines of lower amines Fatty acid (stearic acid, oleic acid, etc.) salts and the like can be mentioned. Examples of the secondary amine salt type include inorganic acid salts and organic acid salts such as ethylene oxide adducts of aliphatic amines. Examples of the tertiary amine salt type include, for example, aliphatic amines (triethylamine, ethyldimethylamine, N, N, N ', N'-tetramethylethylenediamine, etc.), ethylene oxide of aliphatic amine (2 mol). Above) adduct, alicyclic amine (N-methylpyrrolidine, N-methylpiperidine, N-
Methylhexamethyleneimine, N-methylmorpholine,
1,8-diazabicyclo (5,4,0) -7-undecene, etc.), nitrogen-containing heterocyclic aromatic amine (4-dimethylaminopyridine, N-methylimidazole, 4,4′-
Dipyridyl) and inorganic or organic acid salts; inorganic or organic acid salts of tertiary amines such as triethanolamine monostearate and stearamidoethyldiethylmethylethanolamine.

Amphoteric surfactant (S-3) used in the present invention
Examples thereof include carboxylate type amphoteric surfactants, sulfate ester type amphoteric surfactants, sulfonate type amphoteric surfactants, phosphate ester salt type amphoteric surfactants, and the like. Examples of the active agent further include amino acid-type amphoteric surfactants and betaine-type amphoteric surfactants.

Examples of the carboxylate-type amphoteric surfactant include amino acid-type amphoteric surfactant, betaine-type amphoteric surfactant, imidazoline-type amphoteric surfactant, and the like. Among these, the amino acid-type amphoteric surfactant is An amphoteric surfactant having an amino group and a carboxyl group in the molecule, and examples thereof include compounds represented by the following general formula. _{[R-NH- (CH 2)} n-COO] mM [ wherein, R represents a monovalent hydrocarbon group; n is usually 1 or 2;
m is 1 or 2; M is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium cation, an amine cation, an alkanolamine cation, or the like. Specific examples thereof include alkylaminopropionic acid-type amphoteric surfactants (sodium stearylaminopropionate, sodium laurylaminopropionate, etc.); alkylaminoacetic acid-type amphoteric surfactants (sodium laurylaminoacetate, etc.) and the like. To be

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.
Alkyl dimethyl betaine represented by the following general formula (stearyl dimethylamino acetate betaine, lauryl dimethyl amino acetate betaine etc.), amide betaine (coconut oil fatty acid amide propyl betaine etc.), alkyldihydroxyalkyl betaine (lauryl dihydroxyethyl betaine etc.) and the like. To be

Further, examples of the imidazoline type amphoteric surfactant include 2-undecyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine.

Other amphoteric surfactants include, for example, glycine-type amphoteric surfactants such as sodium lauroylglycine, sodium lauryldiaminoethylglycine, lauryldiaminoethylglycine hydrochloride and dioctyldiaminoethylglycine hydrochloride; pentadecylsulfone. Examples thereof include sulfobetaine-type amphoteric surfactants such as taurine.

As the nonionic surfactant (S-4),
Examples thereof include alkylene oxide addition type nonionic surfactants and polyvalent alcohol type nonionic surfactants.

The alkylene oxide addition type nonionic surfactant is a polyalkylene glycol obtained by directly adding alkylene oxide to higher alcohol, higher fatty acid or alkylamine or by adding alkylene oxide to glycols. Obtained by reacting a higher fatty acid or the like with a polyol, or by adding an alkylene oxide to an esterified product obtained by reacting a higher fatty acid with a polyhydric alcohol, or by adding an alkylene oxide to a higher fatty acid amide. To be

Examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide. Preferred among these are ethylene oxide and random or block adducts of ethylene oxide and propylene oxide. The number of moles of alkylene oxide added is 10
˜50 mol is preferred, and the one in which 50 to 100% by weight of the alkylene oxide is ethylene oxide is preferred.

Specific examples of the alkylene oxide addition type nonionic surfactant include oxyalkylene alkyl ethers.
Tell (for example, octyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct,
Oleyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide propylene oxide block adduct, etc.); polyoxyalkylene higher fatty acid ester (eg, stearyl acid ethylene oxide adduct, lauric acid ethylene oxide adduct, etc.);
Polyoxyalkylene polyhydric alcohol higher fatty acid ester (for example, lauric acid diester of polyethylene glycol, oleic acid diester of polyethylene glycol, stearic acid diester of polyethylene glycol, etc.); Polyoxyalkylene alkylphenyl ether (for example, nonylphenol ethylene Oxide adduct, nonylphenol ethylene oxide propylene oxide block adduct, octylphenol ethylene oxide adduct, bisphenol A ethylene oxide adduct, dinonylphenol ethylene oxide adduct, styrenated phenol ethylene oxide adduct, etc.); polyoxyalkylene alkylamino acid Ter and (eg, laurylamine ethylene oxide adduct, stearylamine Ethylene oxide adduct, etc.); polyoxyalkylene alkyl alkanolamides (for example, ethylene oxide adduct of hydroxyethyl lauric acid amide, ethylene oxide adduct of hydroxypropyl oleic acid amide, ethylene oxide adduct of dihydroxyethyl lauric acid amide) Such)
Is mentioned.

Examples of polyhydric alcohol type nonionic surfactants include polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid ester alkylene oxide adducts, polyhydric alcohol alkyl ethers, and polyhydric alcohol alkyl ether alkylene oxide adducts. To be

Specific examples of the polyhydric alcohol fatty acid ester include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitan dilaurate, sorbitan diolate and sucrose mono. Examples include stearates. Specific examples of the polyhydric alcohol fatty acid ester alkylene oxide adduct include ethylene glycol monooleate ethylene oxide adduct, ethylene glycol monostearate ethylene oxide adduct, trimethylolpropane monostearate ethylene oxide propylene oxide random adduct, sorbitan mono. Examples thereof include laurate ethylene oxide adduct, sorbitan monostearate ethylene oxide adduct, sorbitan distearate ethylene oxide adduct, sorbitan dilaurate ethylene oxide propylene oxide random adduct, and the like. Specific 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. Specific examples of the polyhydric alcohol alkyl ether alkylene oxide adduct include sorbitan monostearyl ether ethylene oxide adduct, methyl glycoside ethylene oxide propylene oxide random adduct, lauryl glycoside ethylene oxide adduct, stearyl glycoside ethylene oxide propylene oxide random adduct. And so on.

Examples of the water-soluble polymer (T) include cellulosic compounds (eg, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, arabic. Rubber, chitin, chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymers (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, hydroxylation of polyacrylic acid) Sodium partially neutralized product, sodium acrylate-acrylic acid ester copolymer), styrene-maleic anhydride copolymer Sodium oxide (partial) neutralization product,
Examples thereof include water-soluble polyurethanes (reaction products of polyethylene glycol, polycaprolactone diol, etc. and polyisocyanate, etc.).

The solvent (U) used in the present invention may be added to the aqueous medium as the case requires during emulsification and dispersion, or to the [in the oil phase containing the resin (b)] in the dispersion to be emulsified. good. Specific examples of the solvent (U) include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetralin; n-
Aliphatic or alicyclic hydrocarbon solvents such as hexane, n-heptane, mineral spirits, cyclohexane; halogens such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene. Ester-based solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate; ether-based solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether Solvents; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol, n- Alcoholic solvents such as ropanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; N-methyl Heterocyclic compound-based solvents such as pyrrolidone, and these 2
Examples include mixed solvents of one or more kinds.

The plasticizer (V) may be added to the aqueous medium at the time of emulsification and dispersion, or may be added to [in the oil phase containing the resin (b)] in the dispersion to be emulsified. The plasticizer (V) is not limited at all, and the following are exemplified. (V1) Phthalic acid ester [dibutyl phthalate, dioctyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, etc.]; (V2) Aliphatic dibasic acid ester [adipic acid di-2-
Ethylhexyl, 2-ethylhexyl sebacate, etc.]; (V3) Trimellitic acid ester [tri-2-ethylhexyl trimellitate, trioctyl trimellitate, etc.]; (V4) Phosphoric acid ester [triethyl phosphate, tri-2 phosphate] -Ethylhexyl, tricresyl phosphate, etc.]; (V5) Fatty acid ester [butyl oleate, etc.]; (V6) and mixtures of two or more thereof.

The particle size of the resin particles (A) is usually smaller than the particle size of the resin particles (B). From the viewpoint of particle size uniformity, the particle size ratio [volume average particle size of the resin particles (A)]. ] / [Volume average particle diameter of resin particles (B)] is 0.001 to 0.3
The range is preferably. If the particle size ratio is larger than 0.3, (A) does not efficiently adsorb on the surface of (B), and the particle size distribution of (C) obtained tends to be broad.

The volume average particle size of the resin particles (A) may be appropriately adjusted within the above range of particle size ratios so that the particle size is suitable for obtaining the resin particles (C) having a desired particle size. it can. For example, when it is desired to obtain the resin particles (C) having a volume average particle diameter of 1 μm, the resin particles (C) preferably have a thickness of 0.0005 to 0.3 μm, particularly preferably 0.001 to 0.2 μm. When obtained, preferably 0.005
-3 μm, particularly preferably 0.05-2 μm, 100 μm
When it is desired to obtain m particles (C), it is preferably 0.05
˜30 μm, particularly preferably 0.1 to 20 μm.
The volume average particle size is measured by a laser particle size distribution measuring device L
It can be measured with A-920 (manufactured by Horiba, Ltd.) and Multitizer III (manufactured by Coulter).

The resin (b) of the present invention includes the resin (a)
Similarly to the above, any known resin can be used, and the specific examples thereof can be the same as those in (a). (B) can be appropriately selected depending on the intended use and purpose. Generally, preferred resins (b) include polyurethane resins, epoxy resins, vinyl resins, and polyester resins.

The Mn, melting point, Tg, and SP value of the resin (b) may be adjusted appropriately within the preferred range depending on the application.
For example, when the resin particles (C) and the resin particles (B) are used as a slush molding resin or powder coating, Mn of (b) is used.
Is usually 2,000 to 500,000, preferably 4,000 to
It is 200,000. The melting point of (b) (measured by DSC, hereinafter the melting point is a value measured by DSC) is usually 0 ° C to 200 ° C, preferably 35 ° C to 150 ° C. Tg of (b) is usually −
The temperature is 60 ° C to 100 ° C, preferably -30 ° C to 60 ° C. The SP value of (b) is usually 7 to 18, preferably 8 to
It is 14. When used as a spacer for manufacturing electronic components such as liquid crystal displays, standard particles for electronic measuring machines,
Mn of (b) is usually 20,000 to 10 million, preferably 40,000 to 2 million. Melting point of (b) (measured by DSC, hereinafter melting point is measured by DSC), usually 40 ° C to 30
It is 0 ° C., preferably 70 ° C. to 250 ° C. The Tg of (b) is usually −0 ° C. to 250 ° C., preferably 50 ° C. to 2
It is 00 ° C. The SP value of (b) is usually 8 to 18, preferably 9 to 14. When used as a toner used in electrophotography, electrostatic recording, electrostatic printing, etc., M of (b)
n is usually 1,000 to 5,000,000, preferably 2,000
It is 0 to 500,000. (B) melting point (measured by DSC, hereinafter melting point is measured by DSC), usually 20 ° C to 300 ° C,
The temperature is preferably 80 ° C to 250 ° C. Tg of (b) is usually 20 ° C to 200 ° C, preferably 40 ° C to 200 ° C.
Is. The SP value of (b) is usually 8 to 16, preferably 9 to 14.

In the present invention, the resin (b) or its solvent solution is dispersed in an aqueous dispersion of the resin particles (A) comprising the resin (a), and the resin particles (A) are dispersed in the aqueous dispersion. An aqueous dispersion (X1) of resin particles (C) having a structure in which resin particles (A) are attached to the surface of the resin particles (B) by forming resin particles (B) consisting of the resin (b)
To get Alternatively, the precursor (b0) of the resin (b) or a solvent solution thereof is dispersed in an aqueous dispersion of the resin particles (A) composed of the resin (a), and the precursor (b0) is further reacted. The resin (b) in the aqueous dispersion of the resin particles (A)
By forming the resin particles (B) consisting of the above, an aqueous dispersion (X1) of the resin particles (C) having a structure in which the resin particles (A) are attached to the surface of the resin particles (B) is obtained. When dispersing the resin (b) or a solvent solution thereof, or the precursor (b0) of the resin (b) or a solvent solution thereof, a dispersing device can be used. The disperser used in the present invention is not particularly limited as long as it is a commercially available emulsifier and a disperser, and examples thereof include a homogenizer (manufactured by IKA) and a polytron (manufactured by Kinematica).
Batch type emulsifiers such as TK Auto Homo Mixer (made by Tokushu Kika Kogyo), Ebara Milder (made by Arihara Seisakusho), T
K fill mix, TK pipeline homomixer (made by Tokushu Kika Kogyo Co., Ltd.), colloid mill (made by Shinko Pantec Co., Ltd.), slasher, trigonal wet milling machine (made by Mitsui Miike Kakoki Co., Ltd.), capitron (made by Eurotech Co., Ltd.) ),
Fine flow mill (manufactured by Taiheiyo Kiko Co., Ltd.) and other continuous emulsifiers, Microfluidizer (manufactured by Mizuho Industry Co., Ltd.), Nanomizer (manufactured by Nanomizer Co., Ltd.), high-pressure emulsifier such as APV Gaulin (manufactured by Gaulin Co., Ltd.), film emulsifier ( (Made by Refrigeration Industry Co., Ltd.)
Membrane emulsifiers such as VibroMixer (manufactured by Cryogenic Industry Co., Ltd.) and ultrasonic emulsifiers such as ultrasonic homogenizer (manufactured by Branson). Of these, APV Gaulin, homogenizer, TK Auto Homomixer, Ebara Milder, TK Fillmix, and TK Pipeline Homomixer are preferable from the viewpoint of making the particle size uniform.

When the resin (b) is dispersed in the aqueous medium of the resin particles (A), the resin (b) is preferably a liquid. When the resin (b) is a solid at room temperature, it is dispersed in a liquid state at a temperature higher than the melting point, a solvent solution of (b) is used, a precursor (b0) of (b) or a solvent thereof is used. You may use a solution. Resin (b) or its solvent solution,
Alternatively, the viscosity of the precursor (b0) or its solvent solution is
From the viewpoint of particle size uniformity, it is usually 10 to 50,000 cP (measured with a B-type viscometer), preferably 100 to 10,000 cP. The temperature at the time of dispersion is usually 0 to 150 ° C (under pressure), preferably 5 to 98 ° C. When the viscosity of the dispersion is high, it is preferable to carry out emulsification dispersion by raising the temperature to lower the viscosity to the above preferable range. The solvent used for the solvent solution of the resin (b) and the solvent solution of the precursor (b0) is not particularly limited as long as it can dissolve the resin (b) at room temperature or under heating, and specifically, the solvent ( The same as U) is exemplified. The preferable ones differ depending on the kind of the resin (b), but it is preferable that the SP value difference from the resin (b) is 3 or less. Further, from the viewpoint of particle size uniformity of the resin particles (C),
A solvent that dissolves the resin (b) but does not easily dissolve and swell the resin particles (A) made of the resin (a) is preferable.

The precursor (b0) of the resin (b) is not particularly limited as long as it can be converted into the resin (b) by a chemical reaction. For example, when the resin (b) is a vinyl resin, Examples of (b0) include the above-mentioned vinyl-based monomers (which may be used alone or in combination) and a solvent solution thereof, and the resin (b) is a condensation-based resin (for example, a polyurethane resin or an epoxy resin). , (Polyester resin), (b0) is exemplified by a combination of a reactive group-containing prepolymer (α) and a curing agent (β).

When a vinyl-based monomer is used as the precursor (b0), a method of reacting the precursor (b0) to form the resin (b) is, for example, an oil-soluble initiator, monomers and, if necessary, a solvent ( A method in which an oil phase comprising U) is dispersed and suspended in water in the presence of a water-soluble polymer (T) and a radical polymerization reaction is carried out by heating (so-called suspension polymerization method), monomers and, if necessary, a solvent (U) The resulting oil phase is emulsified in an aqueous dispersion of resin particles (A) containing an emulsifier (the same as the surfactant (S) is exemplified) and a water-soluble initiator, and a radical polymerization reaction is carried out by heating. Examples thereof include a method (so-called emulsion polymerization method).

Examples of the oil-soluble or water-soluble initiator include peroxide type polymerization initiator (I) and azo type polymerization initiator (II). Further, the peroxide-based polymerization initiator (I) and the reducing agent may be used in combination to form the redox-based polymerization initiator (III). Furthermore, (I) to (III)
Two or more of these may be used in combination.

Examples of the (I) peroxide-based polymerization initiator include (I-1) oil-soluble peroxide-based polymerization initiators: acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropyl peroxydicarbonate, di-2- Ethylhexyl Peroxydicarbonate, 2,4-Dichlorobenzoyl Peroxide, t-Butyl Peroxy Vivarate, 3,5,5-Trimethylhexanonyl Peroxide, Octanoyl Peroxide, Decanoyl Peroxide, Lauroyl Peroxide, Stearoyl Peroxide, propionitrile peroxide, succinic acid peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, parac Robben benzoyl peroxide, t-
Butyl peroxyisobutyrate, t-butyl peroxymaleic acid, t-butyl peroxylaurate, cyclohexanone peroxide, t-butyl peroxyisopropyl carbonate, 2,5-dimethyl-
2,5-dibenzoylperoxyhexane, t-butylperoxyacetate, t-butylperoxybenzoate, diisobutyldiperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide,
2,5-dimethyl-2,5-di-t-butylperoxyhexane, t-butylcumyl peroxide, t-butylhydroperoxide, di-t-butylperoxide,
Diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, pinanhydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene peroxide, etc. (I-2) Water-soluble peroxide-based polymerization initiator: Hydrogen peroxide, peracetic acid,
Ammonium persulfate, sodium persulfate, etc.

(II) Azo-based polymerization initiator: (II-1) Oil-soluble azo-based polymerization initiator: 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexane1-carbonitrile, 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-
Azobis-2,4-dimethylvaleronitrile, dimethyl-2,2'-azobis (2-methylpropionate),
1,1'-azobis (1-acetoxy-1-phenylethane), 2,2'-azobis (4-methoxy-2,4-
(II-2) Water-soluble azo polymerization initiator: azobisamidinopropane salt, azobiscyanovaleric acid (salt), 2,2'-azobis [2-methyl-N- (2-
Hydroxyethyl) propionamide] etc.

(III) Redox-type polymerization initiator (III-1) Non-aqueous redox-type polymerization initiator: oil-soluble peroxide such as hydroperoxide, dialkyl peroxide, diacyl peroxide and the like, tertiary amine, naphthenate , Mercaptans, organic metal compounds (triethylaluminum, triethylboron, diethylzinc, etc.) in combination with an oil-soluble reducing agent (III-2) Water-based redox polymerization initiator: persulfate,
A combination of a water-soluble peroxide such as hydrogen peroxide and hydroperoxide and a water-soluble inorganic or organic reducing agent (divalent iron salt, sodium bisulfite, alcohol, polyamine, etc.) can be used.

As the precursor (b0), it is also possible to use a combination of a prepolymer (α) having a reactive group and a curing agent (β). Here, the “reactive group” refers to a group capable of reacting with the curing agent (β). In this case, as a method for reacting the precursor (b0) to form the resin (b), an oil phase containing a reactive group-containing prepolymer (α) and a curing agent (β), and optionally a solvent (U) is used. , The resin particles (A) are dispersed in an aqueous dispersion, and the reactive group-containing prepolymer (α) is reacted with the curing agent (β) by heating to form resin particles (B) consisting of the resin (b). Method;
A reactive group-containing prepolymer (α) or a solvent solution thereof is dispersed in an aqueous dispersion of resin particles (A), and a water-soluble curing agent (β) is added thereto and reacted to form a resin (b). Method for forming resin particles (B); when the reactive group-containing prepolymer (α) is a resin that reacts with water and is cured, the reactive group-containing prepolymer (α) or a solvent solution thereof is used as the resin particles ( Examples thereof include a method of reacting with water by dispersing it in the aqueous dispersion of A) to form the resin particles (B) consisting of (b).

Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (α) and the curing agent (β) include the following. : A combination in which the reactive group of the reactive group-containing prepolymer (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and the curing agent (β) is an active hydrogen group-containing compound (β1). . : A combination in which the reactive group contained in the reactive group-containing prepolymer (α) is an active hydrogen-containing group (α2) and the curing agent (β) is a compound (β2) capable of reacting with the active hydrogen-containing group. Of these, from the viewpoint of reaction rate in water,
Is more preferable. In the above combination, the functional group (α1) capable of reacting with the active hydrogen compound is an isocyanate group (α1a) or a blocked isocyanate group (α1).
b), an epoxy group (α1c), an acid anhydride group (α1d), an acid halide group (α1e), and the like. Of these, preferred are (α1a), (α1b) and (α1c), and particularly preferred are (α1a) and (α1b). The blocked isocyanate group (α1b) refers to an isocyanate group blocked by a blocking agent. Examples of the blocking agent include oximes [acetoxime, methylisobutylketoxime, diethylketoxime, cyclopentanone oxime, cyclohexanone oxime, methylethylketoxime, etc.]; lactams [γ-butyrolactam, ε
-Caprolactam, γ-valerolactam, etc.]; carbon number 1
~ 20 aliphatic alcohols [ethanol, methanol, octanol, etc.]; phenols [phenol, m
-Cresol, xylenol, nonylphenol, etc.];
Active methylene compounds [acetylacetone, ethyl malonate, ethyl acetoacetate, etc.]; basic nitrogen-containing compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.]; and these Mixtures of two or more may be mentioned. Of these, preferred are oximes,
Particularly preferred is methyl ethyl ketoxime.

The skeleton of the reactive group-containing prepolymer (α) includes polyether (αw) and polyester (α
x), epoxy resin (αy) and polyurethane (α
z) and the like. Of these, the preferred one is
(Αx), (αy) and (αz), and particularly preferred are (αx) and (αz). Examples of the polyether (αw) include polyethylene oxide, polypropylene oxide, polybutylene oxide and polytetramethylene oxide. Examples of polyesters (αx) include polycondensates of diols (11) and dicarboxylic acids (13), polylactones (ring-opening polymers of ε-caprolactone), and the like. Epoxy resin (α
y) includes bisphenols (bisphenol A,
Examples thereof include addition condensation products of bisphenol F and bisphenol S) with epichlorohydrin. Examples of polyurethane (αz) include polyaddition products of diol (11) and polyisocyanate (15), and polyaddition products of polyester (αx) and polyisocyanate (15).

Polyester (αx), epoxy resin (α
y), a method of incorporating a reactive group into the polyurethane (αz), etc .: a method of leaving one of two or more constituent components in excess to leave the functional group of the constituent component at the end; A method in which a functional group of a constituent component is left at the end by excessively using one of the above constituent components, and a compound containing a functional group and a reactive group capable of reacting with the remaining functional group is reacted. And so on. In the above method, hydroxyl group-containing polyester prepolymer, carboxyl group-containing polyester prepolymer, acid halide group-containing polyester prepolymer, hydroxyl group-containing epoxy resin prepolymer, epoxy group-containing epoxy resin prepolymer, hydroxyl group-containing polyurethane prepolymer, isocyanate group-containing polyurethane A prepolymer or the like is obtained.
For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is such that the ratio of the polyol (1) to the polycarboxylic acid (2) is the hydroxyl group [OH] and the carboxyl group [CO].
The molar ratio [OH] / [COOH] of OH] is usually 2/1.
To 1/1, preferably 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1. In the case of other skeletons and prepolymers having terminal groups, the ratio is the same except that the constituent components are changed. In the above method, the preprimer obtained in the above method, an isocyanate group-containing prepolymer is obtained by reacting a polyisocyanate, a blocked isocyanate group-containing prepolymer is obtained by reacting a blocked polyisocyanate, poly An epoxy group-containing prepolymer is obtained by reacting epoxide, and an acid anhydride group-containing prepolymer is obtained by reacting a polyanhydride. The amount of the compound containing a functional group and a reactive group is, for example, when a hydroxyl group-containing polyester is reacted with polyisocyanate to obtain an isocyanate group-containing polyester prepolymer,
The ratio of polyisocyanate is the isocyanate group [NC
The molar ratio [NCO] / [OH] of O] to hydroxyl group [OH] of the hydroxyl group-containing polyester is usually 5/1 to 1/1, preferably 4/1 to 1.2 / 1, and more preferably 2. 5 /
It is 1 to 1.5 / 1. In the case of other skeletons and prepolymers having terminal groups, the ratio is the same except that the constituent components are changed.

The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.
8 to 2.5. Within the above range, the molecular weight of the cured product obtained by reacting with the curing agent (β) will be high. The number average molecular weight of the reactive group-containing prepolymer (α) is usually 500 to 30,000, preferably 1,000.
~ 20,000, more preferably 2,000-10,
It is 000. The weight average molecular weight of the reactive group-containing prepolymer (α) is 1,000 to 50,000, preferably 2,000 to 40,000, and more preferably 4,000.
It is 0 to 20,000. The viscosity of the reactive group-containing prepolymer (α) at 100 ° C. is usually 2,000 poise or less, preferably 1,000 poise or less.
Setting it to 2,000 poise or less is preferable in that resin particles (C) having a sharp particle size distribution can be obtained with a small amount of solvent.

As the active hydrogen group-containing compound (β1),
Examples thereof include polyamine (β1a) which may be blocked with a removable compound, polyol (β1b), polymercaptan (β1c) and water (β1d).
Of these, preferred are (β1a) and (β1b)
And (β1d), more preferably (β1d)
a) and (β1d), and particularly preferred are blocked polyamines and (β1d).
Examples of (β1a) include those similar to the polyamine (16). Preferred as (β1a) is 4,
4'-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine and mixtures thereof.

As an example of the case where (β1a) is a polyamine blocked with a removable compound, a polyamine obtained from the above polyamines and ketones having 3 to 8 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Examples thereof include ketimine compounds, aldimine compounds obtained from aldehyde compounds having 2 to 8 carbon atoms (formaldehyde, acetaldehyde), enamine compounds, and oxazolidine compounds.

Examples of the polyol (β1b) are the same as the above-mentioned diol (11) and polyol (12). The diol (11) alone or a mixture of the diol (11) and a small amount of the polyol (12) is preferable. Examples of polymercaptan (β1c) include ethylenedithiol, 1,4-butanedithiol, and 1,6-hexanedithiol.

If necessary, an active hydrogen group-containing compound (β1)
In addition, a reaction terminator (βs) can be used. By using a reaction terminator in combination with (β1) at a fixed ratio,
It is possible to adjust (b) to a predetermined molecular weight. As the reaction terminator (βs), monoamines (diethylamine, dibutylamine, butylamine, laurylamine,
Monoethanolamine, diethanolamine, etc.); Monoamine blocked (ketimine compounds, etc.);
Monools (methanol, ethanol, isopropanol, butanol, phenol); monomercaptans (butyl mercaptan, lauryl mercaptan, etc.); monoisocyanates (lauryl isocyanate, phenyl isocyanate, etc.); monoepoxides (butyl glycidyl ether, etc.) and the like.

As the active hydrogen-containing group (α2) contained in the reactive group-containing prepolymer (α) in the above combination, an amino group (α2a), a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), a mercapto group ( α2c), carboxyl group (α2d) and organic group (α2e) blocked with a compound capable of removing them
And so on. Of these, the preferred one is (α
2a), (α2b) and an organic group (α2e) blocked with a compound capable of leaving an amino group, and (α2b) is particularly preferable. Examples of the organic group blocked with a compound capable of leaving an amino group include (β1
The same thing as the case of a) can be illustrated.

A compound capable of reacting with an active hydrogen-containing group (β
Examples of 2) include polyisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polyanhydride (β2d) and polyacid halide (β2e). Of these, the preferred one is (β2
a) and (β2b), more preferable are:
(Β2a).

As the polyisocyanate (β2a),
Examples of the same as the polyisocyanate (15) are exemplified,
The same applies to the preferred ones. Polyepoxide (β2b)
Examples of the polyepoxide (18) include the same, and preferable ones are also the same.

Examples of the polycarboxylic acid (β2c) include a dicarboxylic acid (β2c-1) and a polycarboxylic acid having a valence of 3 or more (β2c-2), and (β2c-1) alone and (β2c-1) Mixtures of small amounts of (β2c-2) are preferred. Examples of the dicarboxylic acid (β2c-1) are the same as those of the dicarboxylic acid (13), and examples of the polycarboxylic acid are the same as those of the polycarboxylic acid (5), and preferred examples are also the same.

Examples of the polycarboxylic acid anhydride (β2d) include pyromellitic acid anhydride. Examples of the polyacid halides (β2e) include the acid halides (acid chloride, acid bromide, acid iodide) of the above (β2c).
And so on. Furthermore, if necessary, a reaction terminator (βs) can be used together with (β2).

The ratio of the curing agent (β) is the equivalent of the reactive group [α] in the reactive group-containing prepolymer (α) to the equivalent amount of the active hydrogen-containing group [β] in the curing agent (β). The ratio [α] / [β] is usually 1/2 to 2/1, preferably 1.5 / 1 to 1
/1.5, and more preferably 1.2 / 1 to 1 / 1.2. When the curing agent (β) is water (β1d), water is treated as a divalent active hydrogen compound.

The resin (b) obtained by reacting the precursor (b0) composed of the reactive group-containing prepolymer (α) and the curing agent (β) in the aqueous medium is the resin particle (B) and the resin particle (C). It becomes a constituent. The weight average molecular weight of the resin (b) obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) is usually 3,000 or more, preferably 3,000 to 10.
It is, 000,000, and more preferably 5,000 to 1,000,000.

A polymer which does not react with the reactive group-containing prepolymer (α) and the curing agent (β) during the reaction of the reactive group-containing prepolymer (α) and the curing agent (β) in an aqueous medium. A so-called dead polymer] can be contained in the system. In this case, (b) is a mixture of a resin obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) in an aqueous medium, and a resin not reacted.

Other additives (pigment, filler, antistatic agent, colorant, release agent, charge control agent, ultraviolet absorber, antioxidant) are added to the resin (a) and / or the resin (b) of the present invention. Agents, antiblocking agents, heat stabilizers, flame retardants, etc.) may be mixed. As a method of adding other additives to the resin (a) or (b), they may be mixed when forming the aqueous dispersion in an aqueous medium, but may be added in advance with the resin (a) or the resin (b). After mixing the substances, it is more preferable that the mixture is added to and dispersed in an aqueous medium. Further, in the present invention, the additive does not necessarily have to be mixed when the particles are formed in the aqueous medium, and may be added after the particles are formed. For example, after forming particles containing no colorant, the colorant may be added by a known dyeing method, or the above additive may be impregnated together with the solvent (U) and / or the plasticizer (V). .

The amount of the aqueous medium used relative to 100 parts of the resin (b) is usually 50 to 2,000 parts by weight, preferably 10 parts.
It is 0 to 1,000 parts by weight. If it is less than 50 parts by weight, the dispersed state of (b) becomes poor. If it exceeds 2,000 parts by weight, it is not economical.

The elongation and / or crosslinking reaction time depends on the structure of the reactive group of the prepolymer (α) and the curing agent (β).
It is selected according to the reactivity due to the combination of
It is 0 minutes to 40 hours, preferably 30 minutes to 24 hours.
The reaction temperature is generally 0 to 150 ° C., preferably 50 to 1
It is 20 ° C. Further, a known catalyst can be used if necessary. Specifically, for example, in the case of a reaction between an isocyanate and an active hydrogen compound, dibutyltin laurate, dioctyltin laurate and the like can be mentioned.

The resin particles (C) are obtained by adding the resin (b), the solvent solution of the resin (b) and the precursor (b0) of the resin (b) to the aqueous dispersion of the resin particles (A) consisting of the resin (a). ) Or a solvent solution of the precursor (b0) is dispersed,
In the case of 0), the resin having a structure in which the precursor (b0) is reacted to form the resin (b), and the resin particles (A) are attached to the surface of the resin particles (B) made of the resin (b) After forming the aqueous dispersion (X1) of the particles (C), the aqueous dispersion (X
Obtained by removing the aqueous medium from 1). The method for removing the aqueous medium includes: a method for drying the aqueous dispersion (X1) under reduced pressure or normal pressure: a solid-liquid separation using a centrifuge, a spakura filter, a filter press, etc., and drying the obtained powder. Method: Examples include a method of freezing and drying the aqueous dispersion (X1) (so-called freeze-drying). In the above, when the obtained powder is dried, it can be carried out by using known equipment such as a fluidized bed dryer, a reduced pressure dryer, and a circulating air dryer. Further, if necessary, the particles can be classified by using an air classifier or the like to obtain a predetermined particle size distribution.

The resin particles (C) are substantially composed of the small resin particles (A) and the large resin particles (B), and the resin particles (A) exist in a form in which they are attached to the surfaces of the resin particles (B). . When it is desired to increase the adhesive force of both particles, when dispersed in an aqueous medium, the resin particles (A) and the resin particles (B) have positive and negative opposite charges, or the resin particles (A) and the resin particles If the particles (B) have the same charge, the surfactant (S)
Alternatively, a water-soluble polymer (T) having an opposite charge to the resin particles (A) and the resin particles (B) may be used, or the SP value difference between the resin (a) and the resin (b) may be 2 or less. Is effective.

From the viewpoint of uniformity of particle size of the resin particles (C), storage stability, etc., the resin particles (C) are usually 0.01 to 60.
It is preferably composed of 40% to 99.99% by weight of (A), and 0.1 to 50% by weight of (A) and 50 to 99.9% by weight of (B).

From the viewpoint of the particle size uniformity of the resin particles (C), powder fluidity, storage stability, etc., 5% or more of the surface of the resin particles (B) is covered with the resin particles (A). It is preferable that 30% or more of the surface of (B) is covered with (A). The surface coverage can be obtained from the image analysis of an image obtained by a scanning electron microscope (SEM) based on the following formula. Surface coverage (%) = [area of the part covered with the resin particles (A) / area of the part covered with the resin particles (A) +
Area of exposed resin particles (B)] × 100

From the viewpoint of particle size uniformity, the variation coefficient of the volume distribution of the resin particles (C) is preferably 30% or less, more preferably 0.1 to 15%. The value of the volume average particle diameter / number average particle diameter of the resin particles (C) is
It is preferably 1.4 or less, and more preferably 1.0 to 1.2. The volume average particle diameter and the number average particle diameter can be simultaneously measured with Multitizer III (manufactured by Coulter Co.).

The resin particles (C) of the present invention are the resin particles (A) and the resin particles (B), and the resin particles (A).
By changing the coverage of the surface of the resin particles (B), the desired unevenness can be provided on the particle surface. In order to improve the powder fluidity, the BET value specific surface area of (C) is preferably 0.5 to 5.0 m ² / g. The BET specific surface area of the present invention is measured by a specific surface area meter such as QUANTASO.
It was measured using RB (manufactured by Yuasa Ionics) (measurement gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen). Similarly, from the viewpoint of powder fluidity, the surface average center line roughness Ra of (C) is 0.01 to 0.
It is preferably 8 μm. Ra is a value obtained by arithmetically averaging the absolute values of deviations between the roughness curve and its center line,
For example, it can be measured with a scanning probe microscope system (manufactured by Toyo Technica).

The shape of the resin particles (C) is preferably spherical from the viewpoint of powder fluidity, melt leveling property and the like.
In that case, the particles (A) and the particles (B) are also preferably spherical. (C) has a Wadell practical sphericity of 0.
It is preferably 85 to 1.00. In addition, Wadel
l Practical sphericity is obtained from the ratio of the diameter of a circle having an area equal to the projected area of a particle and the diameter of the circle having the smallest area circumscribing the projected image of the particle. The projected image of the particles can be taken by, for example, a scanning electron microscope (SEM).

The aqueous dispersion (X2) of resin particles (B) is
In the aqueous dispersion (X1), after the resin particles (A) and the resin particles (B) attached to each other are released, the resin particles (A) are separated and removed from the aqueous dispersion, or It can be obtained by dissolving the resin particles (A) in the dispersion (X1) without dissolving the resin particles (B). The dissolved material of the resin particles (A) may be separated and removed as necessary. Further, the resin particles (B) are obtained by removing the aqueous medium from the aqueous dispersion (X2). As a method for removing the aqueous medium, the same method as in the case of the resin particles (C) is exemplified. The method for desorbing the resin particles (A) and the resin particles (B) attached to each other in the aqueous dispersion (X1) includes: a method of ultrasonically treating the aqueous dispersion (X1): an aqueous dispersion ( X1) is a large amount of water or methanol,
Method of diluting with water-soluble organic solvent such as ethanol or acetone and giving shear by stirring: Method of adding acid, alkali or inorganic salt to the aqueous dispersion (X1) and giving shear by stirring: aqueous dispersion ( X1) is heated and sheared by stirring: When the aqueous dispersion (X1) contains a solvent [resin (a)]
When the solvent solution and / or the resin (b) solvent solution is dispersed in an aqueous medium, or when the solvent is dissolved in the aqueous medium], the solvent removal method and the like are exemplified.

The method for dissolving the resin particles (A) in the aqueous dispersion (X1) is as follows: The resin (a) has a resin having an acidic functional group such as a carboxyl group, a phosphoric acid group and a sulfonic acid group (generally, Acidic functional group 1
When the molecular weight per unit is preferably 1,000 or less), a method of adding an alkali such as sodium hydroxide, potassium hydroxide, ammonia, DBU or an aqueous solution thereof into the aqueous dispersion (X1): The resin (a) has a basic functional group such as a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium base (generally, the molecular weight per basic functional group is 1,
000 or less), a method of adding an acid such as hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid or an aqueous solution thereof to the aqueous dispersion (X1): the resin (a) is a specific solvent ( When dissolved in U) {Generally, the difference in SP value between resin (a) and solvent (U) is 2.5
The following is preferred}, and a method of adding the specific solvent (U) to the aqueous dispersion (X1) is exemplified.

The method for separating and removing the resin particles (A) or the dissolved product thereof from the aqueous dispersion is: The method of separating the resin particles (B) by centrifugation to remove the resin particles (A) contained in the supernatant or the dissolved product thereof is exemplified.

The resin particles (B) of the present invention are the resin particles (A) to the resin particles (B) in the particle size ratio, and the resin particles (B) formed by the resin particles (A) in the aqueous dispersion (X1). Particle surface by changing the coverage of the surface, the depth of the resin particles (A) embedded in the resin particles (B) side on the resin particle (B) / aqueous medium interface in the aqueous dispersion (X1) Can be smoothed or desired irregularities can be imparted to the particle surface. The coverage of the surface of the resin particles (B) with the resin particles (A) and the depth at which the resin particles (A) are embedded on the resin particle (B) side can be controlled by the following method. : When the aqueous dispersion (X1) is produced, if the resin particles (A) and the resin particles (B) are made to have positive and negative electric charges, the coverage and the depth will increase. In this case, as the electric charges of the resin particles (A) and the resin particles (B) are increased,
Coverage and depth increase. : When the aqueous dispersion (X1) is produced, if the resin particles (A) and the resin particles (B) have the same polarity (both positive or both negative), the coverage is lowered, The depth tends to be smaller. In this case, generally the activator (S) and / or the water-soluble polymer (T) [particularly those having an opposite charge to the resin particles (A) and the resin particles (B)]
Use increases the coverage. When the water-soluble polymer (T) is used, the larger the molecular weight of the water-soluble polymer (T), the smaller the depth. : In the production of the aqueous dispersion (X1), the resin (a) has a resin having an acidic functional group such as a carboxyl group, a phosphoric acid group, a sulfonic acid group (generally, the molecular weight per acidic functional group is 1,000. The following is preferable)
The lower the pH of the aqueous medium, the greater the coverage and depth.
On the contrary, the higher the pH, the smaller the coverage and the depth. : In the production of the aqueous medium (X1), the resin (a) has a basic functional group such as a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base (generally basic). When the molecular weight per functional group is preferably 1,000 or less), the higher the pH of the aqueous medium, the greater the coverage and depth. Conversely, the lower the pH, the smaller the coverage and the depth. : The smaller the SP value difference between the resin (a) and the resin (b), the larger the coverage and the depth.

In order to improve the powder fluidity, the BET value specific surface area of the resin particles (B) is 0.5 to 5.0 m ² /
It is preferable that the surface average center line roughness Ra be 0.
It is preferably from 01 to 0.8 μm. Resin particles (B)
The shape is preferably spherical from the viewpoint of powder fluidity, melt leveling property, etc., and the practical sphericity of Wadell is preferably 0.85 to 1.00, more preferably 0.90 to 1 It is 0.00.

[0106]

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

Production Example 1 47 parts of a styrenated phenol polyethylene oxide adduct (Eleminol HB-12, Sanyo Kasei Co., Ltd.) and bisphenol A diglycidyl ether (Epicoat 828, oil) were placed in a reaction vessel equipped with a stir bar and a thermometer. 232 parts (produced by Chemical Shell Co., Ltd.) were added and uniformly dissolved. Water was added dropwise to the reaction vessel under stirring. When 31 parts of water was added, the system was emulsified white. Further, 224 parts of water was added dropwise to obtain an emulsion (1). After heating to raise the system temperature to 70 ° C., a solution prepared by dissolving 20 parts of ethylenediamine in 446 parts of water was added dropwise over 2 hours while maintaining 70 ° C. After dropping, react at 70 ° C for 5 hours and 90 ° C for 5 hours.
Aging was performed to obtain an amine-cured epoxy resin aqueous dispersion [fine particle dispersion A1]. The volume average particle diameter of [fine particle dispersion A1] measured by a laser particle size distribution measuring apparatus LA-920 (manufactured by Horiba Ltd.) was 0.81 μm. Also,
The step of centrifuging a part of [fine particle dispersion A1], further adding water and centrifuging was repeated twice, and then dried to isolate a resin component. The Tg of the resin component (measured by DSC, the same applies hereinafter for Tg) was 120 ° C.

Production Example 2 Water 683 was placed in a reaction vessel equipped with a stirring rod and a thermometer.
Parts, sodium salt of methacrylic acid ethylene oxide adduct sulfuric acid ester (Eleminol RS-30, manufactured by Sanyo Kasei) 11 parts, styrene 139 parts, methacrylic acid 13
Charged 8 parts and 1 part ammonium persulfate, 400 revolutions /
After stirring for 15 minutes, a white emulsion was obtained. After heating, the system temperature was raised to 75 ° C. and the reaction was carried out for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, followed by vinyl resin (styrene-
An aqueous dispersion [fine particle dispersion A2] of a methacrylic acid-copolymer of sodium methacrylic acid-ethylene oxide adduct sulfate sodium salt was obtained. The volume average particle diameter of [fine particle dispersion A2] measured by LA-920 is 0.15 μm.
Met. A part of [fine particle dispersion A2] was dried to isolate a resin component. The Tg of the resin component was 154 ° C.

Production Example 3 343 parts of a 2 mol adduct of ethylene oxide of bisphenol A, 166 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and the mixture was kept at normal pressure. React at 230 ℃ for 8 hours,
After reacting under a reduced pressure of 10 to 15 mmHg for 5 hours,
After cooling to 110 ° C., 17 parts of isophorone diisocyanate was added to toluene and the reaction was carried out at 110 ° C. for 5 hours. (1)] was obtained. Bisphenol A as above
570 parts of an ethylene oxide 2 mol adduct and 217 parts of terephthalic acid were polycondensed at 230 ° C. for 6 hours under normal pressure to obtain an unmodified polyester having a number average molecular weight of 2,400, a hydroxyl value of 51 and an acid value of 5 [polyester (2). ] Was obtained. 200 parts of [urethane-modified polyester (1)] and 800 parts of [polyester (2)] were dissolved and mixed in 2,000 parts of ethyl acetate to obtain [resin solution 1]. A part of [resin solution 1] was dried under reduced pressure to isolate a resin component. Tg of the resin component is 55
It was ℃. In a beaker, add 500 parts of water and 14 mol of nonylphenol ethylene oxide (Nonipol 2
00, manufactured by Sanyo Kasei Kogyo Co., Ltd.) and uniformly dissolved. T
While stirring at 18,000 rpm with a K type homomixer, [Resin solution 1] was charged and stirred for 15 minutes. Then, this mixed solution was transferred to a reaction vessel equipped with a stir bar and a thermometer,
The temperature is raised to distill off ethyl acetate, the temperature is further raised to 98 ° C., and the reaction is allowed to proceed for 5 hours. A fine particle dispersion A3] was obtained. The volume average particle diameter of [fine particle dispersion A3] measured by LA-920 is
It was 0.21 μm. Further, a step of centrifuging a part of [fine particle dispersion A3], further adding water and centrifuging was repeated twice, and then dried to isolate a resin component. The Tg of the resin component was 64 ° C.

Production Example 4 787 parts of polycaprolactone diol (molecular weight 2,000), polyether diol (molecular weight 4,000, EO content 50) were placed in a reaction vessel equipped with a stir bar and a thermometer.
% By weight, PO content 50% by weight) 800 parts, 12
It was dehydrated under reduced pressure at 0 ° C. The water content after dehydration was 0.05%. Then, 55.5 parts of HDI, 65.5 parts of hydrogenated MDI and 0.6 part of dibutyltin dilaurate were added and the reaction was carried out at 80 ° C. for 5 hours. The product thus obtained is designated as [water-soluble polymer T1]. Then, 100 parts of [fine particle dispersion A],
1 part of [Water-soluble polymer 1] and 107 parts of water were mixed and stirred to obtain a milky white liquid. This is designated as [dispersion liquid 1].

Preparation Example 5 784 parts of water, 136 parts of [fine particle dispersion A2], and 48.5 parts of sodium dodecyldiphenyl ether disulfonate.
% Aqueous solution (“Eleminol MON-7”, manufactured by Sanyo Kasei Kogyo) were mixed and stirred to obtain a milky white liquid. This is designated as [dispersion liquid 2].

Production Example 6 48.5 parts of water 634 parts, [fine particle dispersion A3] 286 parts, and sodium dodecyldiphenyl ether disulfonate 48.5.
% Aqueous solution (“Eleminol MON-7”, manufactured by Sanyo Kasei Co., Ltd.) was mixed and stirred to obtain a milky white liquid. This is designated as [dispersion liquid 3].

Production Example 7 1 part of polyvinyl alcohol ("PVA-235", manufactured by Kuraray Co., Ltd.) was dissolved in 100 parts of water. This is designated as [dispersion liquid 4].

Production Example 8 Polycaprolactone diol having a hydroxyl value of 56 [“Plaxel L220AL”, manufactured by Daicel Chemical Industries, Ltd.] 2, in a reaction vessel equipped with a stir bar and a thermometer.
Then, 000 parts was charged and heated at 110 ° C. under a reduced pressure of 3 mmHg for dehydration for 1 hour. Subsequently, 457 parts of IPDI was added and the reaction was carried out at 110 ° C. for 10 hours to obtain a urethane prepolymer having an isocyanate group at the terminal. The free isocyanate content of the urethane prepolymer is 3.6%
Met. This is designated as [prepolymer 1].

Production Example 9 50 parts of ethylenediamine and 50 parts of MIBK were charged into a reaction vessel equipped with a stir bar and a thermometer, and the mixture was heated at 50 ° C. for 5 hours.
The reaction was carried out over time. The obtained ketimine compound is referred to as [curing agent 1].

Example 1 150 parts of [prepolymer 1] and 6 parts of [curing agent 1] were mixed in a beaker, 250 parts of [dispersion 1] was added, and then an ultra disperser (manufactured by Yamato Scientific Co., Ltd.) ) Was used and mixed at a rotation speed of 9000 rpm for 1 minute. After mixing, the mixed solution is put into a reaction vessel equipped with a stir bar and a thermometer and reacted at 50 ° C. for 10 hours to carry out the aqueous dispersion (X
F1) was obtained. Next, 1 part of antiblocking agent [“Cyroid 978”, manufactured by Fuji Davisson Chemical] and light stabilizer [“DIC-TBS”, manufactured by Dainippon Ink and Chemicals]
0.5 part was added, filtered and dried to obtain resin particles (F1).

Example 2 150 parts of [prepolymer 1], 6 parts of [curing agent 1], and 40 parts of ethyl acetate were mixed in a beaker, and 457 parts of [dispersion 2] were added thereto. Using a mixer (manufactured by Tokushu Kiki Co., Ltd.), the mixture was mixed at a rotation speed of 12,000 rpm for 10 minutes. After mixing, the mixed solution was put into a reaction vessel equipped with a stir bar and a thermometer, and the solvent was removed and the reaction was carried out at 50 ° C. for 10 hours to obtain an aqueous dispersion (XF2). Then, filtration and drying were performed to obtain resin particles (F2).

Example 3 To 100 parts of the aqueous dispersion (XF2), 100 parts of a 5% sodium hydroxide aqueous solution was added, and using a TK homomixer (manufactured by Tokushu Kiki), the temperature was adjusted to 40 ° C. and the rotation speed was 12, 000rp
The particles were mixed for 10 minutes at m to dissolve the fine particles derived from [fine particle dispersion A2] attached to the surface of (F2). Then, the step of centrifuging to remove the supernatant and further adding 100 parts of water and centrifuging was repeated twice and then dried to obtain resin particles (F3).

Example 4 150 parts of [prepolymer 1], 6 parts of [curing agent 1], and 40 parts of ethyl acetate were mixed in a beaker, and 457 parts of [dispersion 3] were added to the beaker. Using a mixer (manufactured by Tokushu Kiki Co., Ltd.), the mixture was mixed at a rotation speed of 12,000 rpm for 10 minutes. After mixing, the mixed solution was put into a reaction vessel equipped with a stir bar and a thermometer, and the solvent was removed and the reaction was carried out at 50 ° C. for 10 hours to obtain an aqueous dispersion (XF4). Then, filtration and drying were performed to obtain resin particles (F4).

Comparative Example 1 [Dispersion 4] in place of [Dispersion 1] in Example 1
In the same manner as in Example 1 except that the resin particles (G
1) was obtained.

Example 5 In a beaker, 240 parts of [resin solution 1], 20 parts of trimethylolpropane tribehenate (melting point 58 ° C., melt viscosity of 24 cps) as a releasing agent, and 4 parts of copper phthalocyanine as a coloring agent were put, 1 at TK homomixer at 50 ℃
The mixture was stirred at 2,000 rpm and uniformly dissolved and dispersed to obtain [Resin Solution 1B]. Deionized water 5 in the beaker
00 parts, [dispersion liquid 1] 500 parts, and sodium dodecylbenzenesulfonate 0.2 part were added and uniformly dissolved. Then, the temperature is raised to 50 ° C., and it is 12,000 with a TK homomixer.
While stirring at rpm, 300 parts of [resin solution 1B] was added and stirred for 10 minutes. Then, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, the temperature was raised to distill off ethyl acetate, the temperature was further raised to 98 ° C., and the reaction was carried out for 5 hours to obtain an aqueous dispersion (XF5). . Then, filtration and drying were performed to obtain resin particles (F5).

Example 6 In a beaker, 240 parts of [resin solution 1], 20 parts of trimethylolpropane tribehenate (melting point 58 ° C., melt viscosity of 24 cps) as a releasing agent, and 4 parts of copper phthalocyanine as a coloring agent were put, 1 at TK homomixer at 50 ℃
The mixture was stirred at 2,000 rpm and uniformly dissolved and dispersed to obtain [Resin Solution 1B]. [Dispersion 2] in a beaker
500 parts was added and uniformly dissolved. Then, the temperature was raised to 50 ° C., and while stirring at 12,000 rpm with a TK homomixer, 214 parts of [resin solution 1B] was charged and stirred for 10 minutes. Then, the mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised to distill off ethyl acetate.
The temperature is raised to 8 ° C. and the reaction is carried out for 5 hours to give an aqueous dispersion (XF
6) was obtained. Then, filtration and drying are performed to obtain resin particles (F6)
Got

Example 7 To 100 parts of the aqueous dispersion (XF6), 100 parts of a 5% sodium hydroxide aqueous solution was added, and using a TK homomixer (manufactured by Tokushu Kiki), the temperature was adjusted to 40 ° C. and the rotation speed was 12, 000rp
The particles were mixed for 10 minutes at m to dissolve the fine particles derived from [fine particle dispersion A2] attached to the surface of (F6). Next, the process of centrifuging to remove the supernatant and further adding 100 parts of water and centrifuging was repeated twice and then dried to obtain resin particles (F7).

Example 8 In a beaker, 240 parts of [resin solution 1], 20 parts of trimethylolpropane tribehenate (melting point 58 ° C., melt viscosity of 24 cps) as a releasing agent, and 4 parts of copper phthalocyanine as a coloring agent were put, 1 at TK homomixer at 50 ℃
The mixture was stirred at 2,000 rpm and uniformly dissolved and dispersed to obtain [Resin Solution 1B]. [Dispersion 3] in a beaker
500 parts was added and uniformly dissolved. Then, the temperature was raised to 50 ° C., and while stirring at 12,000 rpm with a TK homomixer, 214 parts of [resin solution 1B] was charged and stirred for 10 minutes. Then, the mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised to distill off ethyl acetate.
The temperature is raised to 8 ° C. and the reaction is carried out for 5 hours to give an aqueous dispersion (XF
8) was obtained. Then, the resin particles (F8) are separated by filtration and dried.
Got

Comparative Example 2 [Dispersion 4] instead of [Dispersion 1] in Example 5.
In the same manner as in Example 1 except that the resin particles (G
2) was obtained.

Physical Property Measurement Example 1 Resin particles (F) obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were used.
1) to (F8), (G1) and (G2) were dispersed in water and the particle size distribution was measured with a Coulter counter. The coefficient of variation is a value calculated by the formula of (standard deviation / volume average particle size × 100). The surface coverage of each particle, BET
The specific surface area and surface average centerline roughness were measured. The results are shown in Table 1.

[0127]

[Table 1]

[0128]

The method of the present invention has the following effects. 1. A resin particle dispersion and resin particles having a uniform particle size can be obtained without using inorganic fine powder. 2. Since the resin particles are obtained by dispersion in water, the resin particles can be manufactured safely and at low cost as compared with the conventional manufacturing method. 3. Resin particles having excellent powder fluidity and storage stability can be obtained. 4. It is possible to produce resin particles having excellent heat resistance and resin particles that are heated and melted to give a coating film having excellent mechanical properties. From the above effects, the resin dispersion and the resin particles obtained from the production method of the present invention are resins for slush molding, powder coatings, spacers for producing electronic components such as liquid crystal, standard particles for electronic measuring instruments, and electrophotography. It is extremely useful as a resin particle useful as a toner used in electrostatic recording, electrostatic printing, various hot melt adhesives, and other molding materials.

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Claims (24)

(57) [Claims] 1. A resin (b) or a solvent solution thereof, or a precursor (b0) of the resin (b) or a solvent solution thereof is dispersed in an aqueous dispersion of resin particles (A) comprising the resin (a). When the precursor (b0) or a solvent solution thereof is used, the precursor (b0) is further reacted to produce resin particles (resin (b)) in the aqueous dispersion of the resin particles (A) ( By forming B), an aqueous dispersion (X1) of resin particles (C) having a structure in which the resin particles (A) are attached to the surface of the resin particles (B) is formed. A method for producing resin particles, which comprises removing the medium. 2. The resin particles (C) are 0.1 to 50% by weight.
2. The production method according to claim 1, comprising the resin particles (A) of 5 and 50 to 99.9% by weight of the resin particles (B). 3. The method according to claim 1 or 2, wherein the resin particles (C) have a structure in which 5% or more of the surface of the resin particles (B) is covered with the resin particles (A). 4. The production method according to claim 1, wherein the variation coefficient of volume distribution of the resin particles (C) is 0.1 to 15%. 5. The method according to claim 1, wherein the resin particles (C) have a volume average particle diameter / number average particle diameter value of 1.0 to 1.2. 6. The production method according to claim 1, wherein the value of (volume average particle diameter of resin particles (A) / volume average particle diameter of resin particles (B)) is 0.001 to 0.3. . 7. The volume average particle diameter of the resin particles (A) is 0.
It is 01-30 micrometers, and the volume average particle diameter of the resin particle (B) is 0.1-300 micrometers, The manufacturing method in any one of Claims 1-6. 8. A resin (a) and / or a resin (b)
Is at least one resin selected from the group consisting of a polyurethane resin, an epoxy resin, a vinyl resin, and a polyester resin, The production method according to claim 1. 9. The precursor (b0) comprises a prepolymer (α) having a reactive group and a curing agent (β).
The manufacturing method according to any one of 1. 10. The reactive group-containing prepolymer (α) comprises:
The production method according to claim 9, which has at least one reactive group selected from the group consisting of an isocyanate group, a blocked isocyanate group and an epoxy group, and the curing agent (β) is an active hydrogen group-containing compound (β1). . 11. The method according to claim 10, wherein the active hydrogen group-containing compound (β1) is a ketimine compound. 12. The manufacturing method according to claim 1, wherein the melting point of the resin (b) is 0 ° C. to 200 ° C. 13. The resin (b) has a Tg of 20 ° C. to 200 ° C.
The manufacturing method according to any one of claims 1 to 12. 14. The resin (b) is a polyamide resin, a polyimide resin, a silicon resin, a phenol resin, a melamine resin, a urea resin, an aniline resin, an ionomer resin,
And at least one resin selected from the group consisting of polycarbonate resins. 15. The method according to claim 1, wherein the BET value specific surface area is 0.5 to 5.0 m ^2.
/ G resin particles. 16. The surface average centerline roughness Ra is 0.01 to.
The resin particle according to claim 15, which has a size of 0.8 μm. 17. The practical sphericity of Wadell is 0.90.
The resin particles according to claim 15 or 16, which have a particle size of about 1.00. 18. Resin particles (A) comprising the resin (a)
Is a resin particle (C) having a structure formed by adhering to the surface of the resin particle (B) made of the resin (b): Is 0.001 to 0.3, and the volume average particle diameter of the resin particles (A) is 0.01 to 30.
and the volume average particle size of the resin particles (B) is 0.1 to 300 μm, and the value of the volume average particle size / number average particle size of the resin particles (C) is 1.00 to 1.20. And: 5% or more of the surface of the resin particles (B) is the resin particles (A)
The BET value specific surface area of the resin particles (C) is 0.5 to 5.
0 m ² / g, and the surface average center line roughness Ra of the resin particles (C) is 0.0.
1 to 0.8 μm, and: Wadell's practical sphericity of the resin particles (C) is 0.
90 to 1.00, wherein the resin (a) and / or the resin (b) is at least one resin selected from the group consisting of polyurethane resin, epoxy resin, vinyl resin and polyester resin. Resin particles to be used. 19. Resin particles comprising a resin (b), wherein: the value of volume average particle diameter / number average particle diameter of resin particles is 1.0 to 1.20, and: BET value ratio of resin particles Surface area is 0.5-5.0m ²
/ G: The surface average centerline roughness Ra of the resin particles is 0.01 to
0.8 μm: Practical sphericity of resin particles of Wadell is 0.90
1.00: resin particles, wherein the resin (b) is at least one resin selected from the group consisting of polyurethane resin, epoxy resin, vinyl resin and polyester resin. 20. The resin particle according to any one of claims 15 to 19, which is for a slush molding resin. 21. The resin particles according to claim 15, which are for powder coatings. 22. The resin particle according to any one of claims 15 to 19, which is for a spacer for producing an electronic component. 23. The resin particle according to any one of claims 15 to 19, which is for a standard particle of an electronic measuring instrument. 24. The resin particles according to claim 15, which are for electrophotography, electrostatic recording, or electrostatic printing toner.