JP4130639B2 - Method for producing resin dispersion and resin particles - Google Patents

Description

  The present invention relates to a resin dispersion, a method for producing resin particles, and resin particles. More specifically, the present invention relates to resin particles useful for various applications, a method for producing an aqueous resin dispersion thereof, and resin particles.

A resin solution obtained by dissolving a resin in a solvent in advance is dispersed in an aqueous medium in the presence of a dispersing agent (auxiliary) such as a surfactant or a water-soluble polymer, and the solvent is removed by heating or decompression to remove resin particles. There is a method to obtain (dissolving resin suspension method).
Patent Document 1 is known as a method for obtaining a resin dispersion and resin particles having a uniform particle size without using inorganic fine powders by using a dissolved resin suspension method. However, it may be difficult to obtain a stable resin dispersion depending on the composition of the resin raw material, selection of an emulsifier or dispersant, production conditions, and the like.
JP 2002-284881 A

  The present invention has been made in view of the above circumstances in the prior art. That is, an object is to provide a resin dispersion having a uniform particle size and a method for stably producing resin particles.

That is, the present invention is the following four inventions [(V) and (VI) are reference inventions. ]
(I) In the aqueous dispersion (W) of the resin particles (A) made of the resin (a), one type selected from the resin (b), the precursor (b0) of (b), and an organic solvent solution thereof When the oily liquid (O) composed of the above is dispersed and (b0) or a solution thereof is used, (b0) is further reacted, and in the aqueous dispersion of (A), resin particles (b) ( A method for producing an aqueous dispersion (X1) of resin particles (C) having (A) attached to the surface of (B) by forming B), wherein (O) has a weight average molecular weight Contains 1000 or less tertiary amine (c) and has an acid value of 1-50 mg KOH / g, a total amine value of 1-50 mg KOH / g, and a tertiary amine value of 0.1-50 mg KOH / g A method for producing an aqueous resin dispersion characterized by the above.
(II) In the aqueous resin dispersion (X1) obtained by the production method of (I), (A) is separated from the aqueous resin dispersion after removing the adhering (A) and (B). The manufacturing method of the aqueous resin dispersion which obtains the aqueous resin dispersion (X2) of (B) by the method of removing or the method of dissolving (A).
(III) A method for producing resin particles in which an aqueous solvent is removed from an aqueous resin dispersion obtained by the production method of (I) or (II).

(IV) Resin particles obtained by the production method of (III).
(V) 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),
[1] [Volume average particle diameter of (A) / Volume average particle diameter of (B)] is 0.001 to 0.3,
[2] The volume average particle diameter of (A) is 0.0005 to 30 μm, and the volume average particle diameter of (B) is 0.1 to 300 μm.
[3] 5% or more of the surface of (B) is covered with (A),
[4] The [volume average particle diameter / number average particle diameter] of (C) is 1.0 to 1.5,
[5] The tertiary amine content of (C) is 10 to 500 ppm,
[6] Resin particles wherein (a) and / or (b) is one or more resins selected from the group consisting of polyurethane resins, epoxy resins, vinyl resins and polyester resins.
(VI) Resin particles (B) made of resin (b),
[1] The [volume average particle size / number average particle size] of (B) is 1.0 to 1.5,
[2] The volume average particle size of (B) is 0.1 to 300 μm,
[3] The tertiary amine content of (B) is 10 to 500 ppm,
[4] Resin particles wherein (b) is one or more resins selected from the group consisting of polyurethane resins, epoxy resins, vinyl resins and polyester resins.

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 stably produced without using inorganic fine powder.
2. Since resin particles are obtained by dispersion in water, the resin particles can be produced safely and at low cost.
3. Resin particles having excellent powder flowability and storage stability can be obtained.
4). Resin particles excellent in heat resistance and resin particles that give a coating film excellent in mechanical properties by heating and melting can be produced.
5. Resin for slush molding, powder coatings, spacers for manufacturing electronic parts such as liquid crystal, standard particles for electronic measuring equipment, toner used for electrophotography, electrostatic recording, electrostatic printing, various hot melt adhesives, other molding materials Thus, resin particles useful for various applications can be provided.

The present invention is described in detail below.
In the present invention, as the resin (a) contained in the resin particles (A), any resin that can form an aqueous dispersion can be used, and even a thermoplastic resin is thermosetting. Resin may be used. 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, etc. Is mentioned. As the resin (a), two or more of the above resins may be used in combination. Among these, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, and a combination thereof are preferable from the viewpoint that an aqueous resin dispersion of fine spherical resin particles is easily obtained, and a vinyl resin and a polyurethane resin are more preferable. , Polyester resins and combinations thereof.

Among the resins (a), preferable resins, that is, vinyl resins, polyurethanes, epoxy resins and polyesters will be described, but other resins can be used in the same manner.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. A known polymerization catalyst or the like can be used for the polymerization.
Examples of the vinyl monomer include the following (1) to (10).

(1) Vinyl hydrocarbons:
(1-1) Aliphatic vinyl hydrocarbon: Alkene having 2 to 12 carbon atoms (for example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, and α-olefin having 3 to 24 carbon atoms) Etc.); C4-12 alkadienes (for example, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, etc.).
(1-2) Alicyclic vinyl hydrocarbon: mono- or di-cycloalkene having 6 to 15 carbon atoms (such as cyclohexene, vinylcyclohexene and ethylidenebicycloheptene), mono- or di- having 5 to 12 carbon atoms Cycloalkadienes (eg, (di) cyclopentadiene, etc.); and terpenes (eg, pinene, limonene, indene, etc.) and the like.
(1-3) Aromatic vinyl hydrocarbon: styrene; hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl having 1 to 24 carbon atoms) substituted styrene (for example, α-methylstyrene, vinyltoluene, 2 , 4-dimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene and trivinyl benzene); and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomers and their salts:
C3-C30 unsaturated monocarboxylic acid (for example, (meth) acrylic acid (representing acrylic acid and / or methacrylic acid; the same expression is used hereinafter), isocrotonic acid, cinnamic acid, etc.) 3-30 unsaturated dicarboxylic acids (anhydrides) (e.g. (anhydrous) maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid and mesaconic acid, etc.); and unsaturated dicarboxylic acids having 3 to 30 carbon atoms Monoalkyl (carbon number 1 to 24) ester (for example, maleic acid monomethyl ester, maleic acid monooctadecyl ester, fumaric acid monoethyl ester, itaconic acid monobutyl ester, itaconic acid glycol monoether, citraconic acid monoeicosyl ester, etc.) etc.
Examples of the salt of the carboxyl group-containing vinyl monomer include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, and quaternary ammonium salts. . The amine salt is not particularly limited as long as it is an amine compound. For example, a primary amine salt (ethylamine salt, butylamine salt, octylamine salt, etc.), secondary amine (diethylamine salt, dibutylamine salt, etc.), tertiary amine, etc. (Triethylamine salt, tributylamine salt, etc.). Examples of the quaternary ammonium salt include tetraethylammonium salt, triethyllaurylammonium salt, tetrabutylammonium salt, tributyllaurylammonium salt and the like.
Specific examples of the carboxyl group-containing vinyl monomer salt include sodium acrylate, sodium methacrylate, monosodium maleate, disodium maleate, potassium acrylate, potassium methacrylate, monopotassium maleate, lithium acrylate, acrylic acid Examples include cesium, ammonium acrylate, calcium acrylate, and aluminum acrylate.

(3) Sulfo group-containing vinyl monomers and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms (for example, vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid); styrene sulfonic acid and alkyl (2 to 24 carbon) derivatives thereof (for example, α-methyl styrene sulfone) Acid etc .; C5-C18 sulfo (hydroxy) alkyl- (meth) acrylate (for example, sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloyl) Oxyethanesulfonic acid and 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, etc.); C5-C18 sulfo (hydroxy) alkyl (meth) acrylamide (for example, 2- (meth) acryloylamino-2, 2-dimethylethanesulfonic acid, 2- (meth) (Crylamido-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid); alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid (for example, propylallylsulfosuccinic acid, butylallylsulfosuccinic acid, 2- Ethylhexyl-allylsulfosuccinic acid); poly [n (degree of polymerization, the same shall apply hereinafter) = 2 to 30] oxyalkylene (oxyethylene, oxypropylene, oxybutylene: single, random or block) sulfate of mono (meth) acrylate [For example, poly (n = 5 to 15) oxyethylene monomethacrylate sulfate, poly (n = 5 to 15) oxypropylene monomethacrylate sulfate, etc.]; in the following general formulas (3-1) to (3-3) Compounds represented; and salts thereof, etc. Is mentioned.
In addition, as the salt, (2) carboxyl group-containing vinyl monomers and counter ions shown in the salts are used.

O (AO) nSO ₃ H
｜
_{CH 2 = CHCH 2 OCH 2 CHCH} 2 O-Ar-R (3-1)

CH ₂ = CHCH ₃
｜
R-Ar-O (AO) nSO 3 H (3-2)

CH ₂ COOR '
｜
HO ₃ SCHCOOCH ₂ CH (OH) CH ₂ OCH ₂ CH═CH ₂ (3-3)
(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. 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) Phosphono group-containing vinyl monomer and salt thereof:
(Meth) acryloyloxyalkyl phosphate monoester (alkyl group having 1 to 24 carbon atoms) (for example, 2-hydroxyethyl (meth) acryloyl phosphate and phenyl-2-acryloyloxyethyl phosphate), (meth) acryloyloxy Alkylphosphonic acid (alkyl group having 1 to 24 carbon atoms) (for example, 2-acryloyloxyethylphosphonic acid).
In addition, as the salt, (2) carboxyl group-containing vinyl monomers and counter ions shown in the salts are used.

(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-butylaminoethyl 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, amino Indole, aminopyrrole, aminoimidazole, aminomercaptothiazole, salts thereof, etc. (6-2) Amido group-containing vinyl monomer:
(Meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide, N, N -Dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc. (6-3) Nitrile group-containing vinyl monomer having 3 to 10 carbon atoms:
(Meth) acrylonitrile, cyanostyrene, cyanoacrylate, etc. (6-4) Vinyl monomer containing a group consisting of a quaternary ammonium cation:
Quaternized products of tertiary amino group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, etc. (methyl chloride, dimethyl sulfate, benzyl) Quaternized with a quaternizing agent such as chloride or dimethyl carbonate (for example, dimethyldiallylammonium chloride, trimethylallylammonium chloride).
(6-5) Nitro group-containing vinyl monomer having 8 to 12 carbon atoms:
Nitrostyrene etc.

(7) Epoxy group-containing vinyl monomer having 6 to 18 carbon atoms:
Glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc.

(8) Halogen element-containing vinyl monomer having 2 to 16 carbon atoms:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, etc.

(9) Vinyl ester, vinyl (thio) ether, vinyl ketone, vinyl sulfone:
(9-1) A vinyl ester having 4 to 16 carbon atoms,
For example, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl 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, Kosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two alkyl groups) Group is a linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, Tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] and other vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylate, Methyl alcohol ethylene oxide (hereinafter, ethylene oxide is referred to as EO) 1 0 mol adduct (meth) acrylate, lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate 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, etc.], etc .;
(9-2) Vinyl (thio) ether having 3 to 16 carbon atoms,
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 having 4 to 12 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone);
C2-C16 vinyl sulfone (for example, 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.

  Among the vinyl resins, as a polymer obtained by copolymerizing vinyl monomers (copolymer of vinyl monomers), any one of the above monomers (1) to (10) may be binary or more in any proportion. For example, styrene- (meth) acrylic acid ester copolymer, styrene-butadiene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-acrylonitrile copolymer Copolymers, styrene- (maleic anhydride) copolymers, styrene- (meth) acrylic acid copolymers, styrene- (meth) acrylic acid-divinylbenzene copolymers, and styrene-styrenesulfonic acid- (meth) acrylic acid esters A copolymer etc. are mentioned.

Since the resin (a) needs to form the resin particles (A) in the aqueous resin dispersion, the resin (a) is in water at least under the conditions (usually 5 to 90 ° C.) for forming the aqueous resin dispersion (X1). It is necessary that it is not completely dissolved. Therefore, when the vinyl resin is a copolymer, the ratio between the hydrophobic monomer and the hydrophilic monomer constituting the vinyl resin depends on the type of monomer selected, but generally the hydrophobic monomer is 10% or more. It is preferable that it is 30% or more. If the ratio of the hydrophobic monomer is 10% or less, the vinyl resin is likely to be water-soluble, and the particle size uniformity of (C) may be impaired.
Here, the hydrophilic monomer means a monomer that dissolves 100 g or more in 100 g of water at 25 ° C., and the hydrophobic monomer means another monomer (a monomer that does not dissolve 100 g or more in 100 g of water at 25 ° C.). The same applies to the other resin.)

As the polyester resin, a polycondensate of a polyol with a polycarboxylic acid, an acid anhydride thereof, or a lower alkyl (carbon group having 1 to 4 carbon atoms) can be used.
A known polycondensation catalyst or the like can be used for the polycondensation reaction.
As the polyol, a diol (11) and a tri- or octavalent or higher polyol (12) are used.
As the polycarboxylic acid, its acid anhydride or lower alkyl ester, dicarboxylic acid (13), tri- or hexavalent or higher polycarboxylic acid (14), these acid anhydrides and lower alkyl esters are used.
The ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1 as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1/1, particularly preferably 1.3 / 1 to 1.02 / 1.

Examples of the diol (11) include alkylene glycols having 2 to 30 carbon atoms (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octane). Diol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol and 2,2-diethyl-1,3-propanediol, etc .; alkylene ether glycols having a molecular weight of 106 to 10,000 (for example, diethylene glycol, triethylene glycol, dipropylene glycol) Polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol); alicyclic diols having 6 to 24 carbon atoms (for example, 1,4-cyclohexanedimethanol and Alkylene oxide of the above alicyclic diol having a molecular weight of 100 to 10,000 (hereinafter referred to as AO) [EO, propylene oxide (hereinafter referred to as PO), butylene oxide (hereinafter referred to as BO). Adducts (added mole number 2 to 100) (for example, EO 10 mol adduct of 1,4-cyclohexanedimethanol, etc.); bisphenols having 15 to 30 carbon atoms (bisphenol A, bisphenol F, bisphenol S, etc.) ) Or AO (EO, PO, BO, etc.) adducts of polyphenols having 12 to 24 carbon atoms (for example, catechol, hydroquinone, resorcin, etc.) (addition mole number 2 to 100) (for example, bisphenol A · EO 2 to 4 mole addition) Products, bisphenol A · PO2-4 mol adducts, etc.); Weight average polylactone diol of molecular weight 100 to 5000 (e.g., poly ε- caprolactone diol); polybutadiene diol having a weight-average molecular weight 1,000 to 20,000 and the like.
Of these, AO adducts of alkylene glycol and bisphenols are preferred, more preferably AO adducts of bisphenols, and mixtures thereof with alkylene glycols.

As the polyol (12) having 3 to 8 or more valences, an aliphatic polyhydric alcohol having 3 to 8 or more and 3 to 8 carbon atoms (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, Sorbitan and sorbitol); AO (carbon number 2 to 4) adduct (2 to 100 moles added) of trisphenol having 25 to 50 carbon atoms (for example, trisphenol PA and the like) (for example, trisphenol PA · EO 2 to 2). 4 mol adduct, trisphenol PA · PO 2-4 mol adduct, etc.); AO (carbon number 2-4) adduct (addition mol) of novolak resins having a polymerization degree of 3-50 (for example, phenol novolak and cresol novolak, etc.) 2-100) (phenol novolak PO 2 mol adduct, phenol novolak E 4 mol adduct); AO (carbon number 2 to 4) adduct (2 to 100 mol added) of polyphenols having 6 to 30 carbon atoms (for example, pyrogallol, phloroglucinol and 1,2,4-benzenetriol, etc.) ) (Pyrogallol EO 4 mole adduct); and acrylic polyols having a polymerization degree of 20 to 2000 [copolymerization of hydroxyethyl (meth) acrylate with other vinyl monomers (for example, styrene, (meth) acrylic acid, (meth) acrylic acid ester, etc.) Polymer, etc.].
Of these, AO adducts of aliphatic polyhydric alcohols and novolac resins are preferred, and AO adducts of novolak resins are more preferred.

Examples of the dicarboxylic acid (13) include alkane dicarboxylic acids having 4 to 32 carbon atoms (for example, succinic acid, adipic acid, sebacic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and octadecanedicarboxylic acid); Alkenedicarboxylic acids (for example, maleic acid, fumaric acid, citraconic acid and mesaconic acid); branched alkenedicarboxylic acids having 8 to 40 carbon atoms [for example, dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid) Branched alkane dicarboxylic acids having 12 to 40 carbon atoms [eg, alkyl succinic acids (decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid, etc.); aromatic dicarboxylic acids having 8 to 20 carbon atoms] (For example, phthalic acid, isophthalic acid, terephthalic acid And naphthalene dicarboxylic acid) and the like.
Of these, alkene dicarboxylic acids and aromatic dicarboxylic acids are preferred, and aromatic dicarboxylic acids are more preferred.
Examples of the tri- or hexavalent or higher polycarboxylic acid (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (for example, trimellitic acid and pyromellitic acid).
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).
Examples of the acid anhydride of the dicarboxylic acid (13) or the tri- or hexavalent or higher polycarboxylic acid (14) include trimellitic acid anhydride and pyromellitic acid anhydride. Examples of these lower alkyl esters include methyl esters, ethyl esters, and isopropyl esters.

  As the polyurethane resin, polyisocyanate (15) and active hydrogen group-containing compound (D) {water, polyol [the diol (11) and trivalent or higher polyol (12)], dicarboxylic acid (13), trivalent or higher Polycarboxylic acid (14), polyamine (16), polythiol (17) and the like} and the like.

  As polyisocyanate (15), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 alicyclic (except for carbon in NCO group) Formula polyisocyanate, aromatic aliphatic polyisocyanate 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, isocyanurate group, Oxazolidone group-containing modified products) 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 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with an aromatic amine (aniline) or a mixture thereof; %) Of trifunctional or higher polyamines] phosgenates: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate Such as theft and the like.
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-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate And aliphatic polyisocyanates.
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.
Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.
Examples of the modified polyisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified polyisocyanates such as urethane-modified TDI, and mixtures of two or more of these [for example, modified MDI and urethane-modified TDI (Combined use with an isocyanate-containing prepolymer)] is included.
Of these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

Examples of the polyamine (16) include aliphatic polyamines (C2 to C18): [1] aliphatic polyamine {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) , Polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; [2] these alkyls (C1-C4 ) Or substituted hydroxyalkyl (C2-C4) [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexa Methylenediamine, methyliminobispropylamine, etc.]; [3] Alicyclic or heterocyclic aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5, 5] Undecane etc.]; [4] Aromatic ring-containing aliphatic amines (C8-C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.),
Alicyclic polyamines (C4 to C15): heterocyclic polyamines (C4 to C15) such as 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline) ): Piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, etc.

Aromatic polyamines (C6-C20): [1] 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 .; aromatic polyamines having a nuclear substituted alkyl group (C1-C4 alkyl groups such as methyl, ethyl, n- and i-propyl, butyl, etc.), for example 2,4- and 2 , 6-Tolylenediamine, Crudetolylenediamine, Diethyltolylene Diamine, 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-diamino Benzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl Til-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-diam Nodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'- Diaminobenzophenone, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5 , 5'-tetraisopropyl-4,4'-diaminodiphenylsulfone, etc.], and mixtures of these isomers in various proportions; [3] nuclear substituted electron withdrawing groups (halogens such as Cl, Br, I, F; Aromatic polyamines having alkoxy groups such as methoxy and ethoxy; nitro groups, etc. [methylene bis-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) se Nido, 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.]; [4] aromatic polyamine having a secondary amino group [the above-mentioned [1] to [3] some or all of -NH ₂ of the aromatic polyamines Is replaced by —NH—R ′ (R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino -4-aminobenzene, etc.], polyamide polyamine: dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) polyamines (the above alkylene dia Emissions, such as low molecular weight polyamide polyamines obtained by condensation of polyalkylene polyamines, etc.), polyether polyamines such as hydrides of cyanoethylation products of polyether polyols (polyalkylene glycol and the like).

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

  Examples of the epoxy resin include a ring-opening polymer of polyepoxide (18), polyepoxide (18) and active hydrogen group-containing compound (D) {water, polyol [the diol (11) and a trivalent or higher valent polyol (12)], dicarboxylic acid. Acid (13), trivalent or higher polycarboxylic acid (14), polyamine (16), polythiol (17), etc.} polyaddition product, or polyepoxide (18) and dicarboxylic acid (13) or higher polyvalent polyvalent acid. Examples include cured products of carboxylic acid (14) with acid anhydrides.

  The polyepoxide (18) of the present invention is not particularly limited as long as it has two or more epoxy groups in the molecule. What has preferable 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material as a preferable polyepoxide (18). The epoxy equivalent of the polyepoxide (18) (molecular weight per epoxy group) is usually 65 to 1000, preferably 90 to 500. When the epoxy equivalent exceeds 1000, the cross-linked structure becomes loose and the physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are deteriorated. On the other hand, it is difficult to synthesize 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 the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols.
Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl di Glycidyl ether, tetramethylbiphenyl diglycidyl ether Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, phenol Or cresol novolak resin, glycidyl ether of limonenephenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained by condensation reactions and polyglycidyl ethers of polyphenols obtained by condensation reactions 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′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like.
Further, in the present invention, the aromatic system is obtained by reacting a polyol with the above-mentioned two reactants, such as triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol. The glycidyl group-containing polyurethane (pre) polymer and an AO (EO or PO) adduct of bisphenol A are also included.

Heterocyclic polyepoxy compounds include trisglycidyl melamine;
Examples of the alicyclic polyepoxy compound include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy- 6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,4-epoxy-6-methyl) (Cyclohexylmethyl) butylamine, dimer acid diglycidyl ester and the like. The alicyclic group also includes a nuclear hydrogenated product of the aromatic polyepoxide compound;
Examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines.

Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether Can be mentioned.
Examples of the polyglycidyl ester of polyvalent 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 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. Two or more of the polyepoxides of the present invention may be used in combination.

  In the production method of the present invention, a resin solution (b), a solvent solution of (b), and a precursor (b0) of (b) in an aqueous dispersion (W) of resin particles (A) comprising the resin (a). And an oily liquid (O) composed of one or more selected from the solvent solution of (b0), and if necessary, the reaction of (b0) is carried out to form the resin particles (B) (A ) Is adsorbed on the surface of (B) to prevent the resin particles (B) or the resin particles (C) from uniting, and (C) is less likely to be split under high shear conditions. Thereby, the particle diameter of (C) is converged to a constant value, and the effect of improving the uniformity of the particle diameter is exhibited. Therefore, (A) has a strength not to be destroyed by shearing at the temperature at which it is dispersed, is not easily dissolved or swelled in water, is dissolved in an oily liquid (W), or swells. It is a preferable characteristic that it is difficult to distort.

  The glass transition temperature (Tg) of the resin (a) is usually 0 ° C. to 300 ° C., preferably from the viewpoints of particle size uniformity, powder flowability, heat resistance during storage, and stress resistance of the resin particles (C). Is 20 ° C to 250 ° C, more preferably 50 ° C to 200 ° C. If the Tg is lower than the temperature at which the aqueous resin dispersion (X1) is produced, the effect of preventing coalescence or preventing splitting is reduced, and the effect of increasing the uniformity of particle size is reduced. In addition, Tg in this invention is a value calculated | required from DSC measurement.

  In Shore D hardness which is a standard of hardness, the hardness of the resin particles (A) is preferably 30 or more, particularly preferably in the range of 45 to 100. Moreover, it is preferable that the hardness when immersed in water or in a solvent for a certain time is also in the above range.

  From the viewpoint of reducing dissolution or swelling of the resin particles (A) with respect to water or a solvent used during dispersion, the molecular weight of the resin (a), SP value (SP value calculation method is Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154), crystallinity, molecular weight between cross-linking points, and the like are preferably adjusted as appropriate.

The number average molecular weight (measured by gel permeation chromatography, hereinafter abbreviated as Mn) of the resin (a) is usually 2-5 million, preferably 2,000-500,000, and the SP value is preferably 7-18. More preferably, it is 8-14. The melting point (measured by DSC) of the resin (a) is preferably 50 ° C. or higher, more preferably 80 ° C. or higher. Moreover, when it is desired 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 cross-linked structure may be any cross-linked form such as covalent bond, coordinate bond, ionic bond, hydrogen bond, and the like. The molecular weight between crosslinking points when a crosslinked structure is introduced into (a) 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 resin dispersion (X2) of the resin particles (B), it is preferable not to introduce a crosslinked structure.

Although the method to make resin (a) the aqueous dispersion of resin particle (A) is not specifically limited, The following [1]-[8] are mentioned.
[1] In the case of a vinyl resin, an aqueous dispersion of resin particles (A) is directly produced by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method using a monomer as a starting material. Process [2] In the case of polyaddition or condensation resins such as polyester resins, polyurethane resins, and epoxy resins, precursors (monomers, oligomers, etc.) or solvent solutions thereof are present in an aqueous medium in the presence of an appropriate dispersant. (3) A method for producing an aqueous resin dispersion of resin particles (A) by heating or adding a curing agent thereafter, and [3] polyaddition of polyester resin, polyurethane resin, epoxy resin, etc. In the case of a condensation resin, a precursor (monomer, oligomer, etc.) or a solvent solution thereof (preferably liquid). A suitable emulsifier is dissolved in water, and then water is added to perform phase inversion emulsification. [4] Any polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) The resin prepared by the polymerization reaction mode may be pulverized using a mechanical pulverizer such as a mechanical rotary type or a jet type, and then spheronized to obtain resin particles, and then an appropriate dispersant. Method of dispersing in water in the presence [5] Resin prepared in advance by polymerization reaction (may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization) A method in which resin particles are obtained by spraying a dissolved resin solution in the form of a mist, and then the resin particles are dispersed in water in the presence of an appropriate dispersant [6] Polymerization reaction (addition polymerization, ring-opening polymerization, Polyaddition, addition condensation, condensation polymerization, etc. The resin particles may be precipitated by adding a poor solvent to a resin solution prepared by dissolving a resin prepared in a solvent in a solvent, or by cooling a resin solution previously dissolved in a solvent. Then, after removing the solvent to obtain resin particles, the resin particles are dispersed in water in the presence of a suitable dispersant. [7] Polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation) in advance A resin solution prepared by dissolving a resin prepared by a polymerization polymerization method in a solvent in a solvent is dispersed in an aqueous medium in the presence of an appropriate dispersant, and this is heated or reduced in pressure. [8] A resin prepared in advance by a polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc. may be used) may be dissolved in the solvent. Shi After dissolving an appropriate emulsifier in tree butter solution, a method of phase inversion emulsification by adding water

  In the above methods [1] to [8], as the emulsifier or dispersant used in combination, a known surfactant (S), water-soluble polymer (T) and the like can be used. Moreover, a solvent (U), a plasticizer (V), etc. can be used together as an auxiliary agent for emulsification or dispersion.

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

  Examples of the anionic surfactant (S-1) include carboxylic acids or salts thereof, sulfate esters, carboxymethylated salts, sulfonates, and phosphate esters.

  Examples of carboxylic acids or salts thereof include saturated or unsaturated fatty acids having 8 to 22 carbon atoms or salts thereof. Specifically, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. , Oleic acid, linoleic acid, ricinoleic acid and a mixture 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.

Examples of sulfate salts include higher alcohol sulfate esters (sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms), higher alkyl ether sulfate esters (EO 1 to 10 mol adducts of aliphatic alcohols having 8 to 18 carbon atoms). Sulfate salts), sulfated oils (natural unsaturated fats or unsaturated waxes that have been neutralized by sulfation), sulfated fatty acid esters (lower alcohol esters of unsaturated fatty acids were neutralized by sulfation) And sulfated olefins (sulfurized and neutralized olefins having 12 to 18 carbon atoms). Examples of the salt include sodium salt, potassium salt, ammonium salt, and alkanolamine salt.
Specific examples of higher alcohol sulfates include octyl alcohol sulfate, decyl alcohol sulfate, lauryl alcohol sulfate, stearyl alcohol sulfate, alcohols synthesized using Ziegler catalysts (for example, ALFOL 1214: CONDEA's sulfate ester salt, alcohols synthesized by the oxo method (for example, Dovanol 23, 25, 45: Mitsubishi Yuka, Tridecanol: Kyowa Hakko, Oxocol 1213, 1215, 1415: Nissan Chemical, Diadol 115 -L, 115H, 135: manufactured by Mitsubishi Kasei) Specific examples of higher alkyl ether sulfates include lauryl alcohol EO 2 mol adduct sulfate ester, octyl alcohol EO 3 mol adduct sulfate Steal salt; Specific examples of sulfated oils include sodium, potassium, ammonium, and alkanolamine salts of sulfated fatty acid esters such as castor oil, peanut oil, olive oil, rapeseed oil, beef tallow, and sheep fat. Sodium, potassium, ammonium, and alkanolamine salts of sulfates such as butyl oleate and butyl ricinoleate; specific examples of sulfated olefins include Thipol (manufactured by Shell).

Examples of the carboxymethylated salt include a carboxymethylated salt of an aliphatic alcohol having 8 to 16 carbon atoms and a carboxymethylated salt of an EO 1 to 10 mol adduct of an aliphatic alcohol having 8 to 16 carbon atoms.
Specific examples of carboxymethylated salts of aliphatic alcohols include octyl alcohol carboxymethylated sodium salt, decyl alcohol carboxymethylated sodium salt, lauryl alcohol carboxymethylated sodium salt, dovanol 23 carboxymethylated sodium salt, tridecanol Specific examples of carboxymethylated sodium salt, carboxymethylated salt of EO 1-10 mol adduct of aliphatic alcohol include octyl alcohol EO3 mol adduct carboxymethylated sodium salt, lauryl alcohol EO4 mol adduct carboxymethylated Examples thereof include sodium salt, dovanol 23 EO 3 mol adduct carboxymethylated sodium salt, tridecanol EO 5 mol adduct carboxymethylated sodium salt and the like.

Examples of the sulfonate include (d1) alkylbenzene sulfonate, (d2) alkylnaphthalene sulfonate, (d3) sulfosuccinic acid diester type, (d4) α-olefin sulfonate, (d5) Igepon T type, (d6 ) Other sulfonates of aromatic ring-containing compounds.
Specific examples of alkylbenzene sulfonate include sodium dodecylbenzene sulfonate; specific examples of alkyl naphthalene sulfonate; sodium dodecyl naphthalene sulfonate; specific examples of sulfosuccinic acid diester type include sulfo-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 phenol sulfonate, and the like.

  Examples of phosphoric acid ester salts include (e1) higher alcohol phosphoric acid ester salts and (e2) higher alcohol EO adduct phosphoric acid ester salts.

  Specific examples of higher alcohol phosphoric acid ester salts include lauryl alcohol phosphoric acid monoester disodium salt, lauryl alcohol phosphoric acid diester sodium salt; specific examples of higher alcohol EO adduct phosphoric acid ester salts include addition of 5 moles of oleyl alcohol EO Phosphoric acid monoester disodium salt.

  Examples of the cationic surfactant (S-2) include a quaternary ammonium salt type and an amine salt type.

  The quaternary ammonium salt type is obtained by reacting a tertiary amine with a quaternizing agent (an alkylating agent such as methyl chloride, methyl bromide, ethyl chloride, benzyl chloride, dimethyl sulfate; EO, etc.). , Lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), cetylpyridinium chloride, polyoxyethylenetrimethylammonium chloride, stearamide ethyl diethylmethyl Examples include ammonium methosulphate.

As amine salt type, primary to tertiary amines are 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, alkylphosphoric acid, etc.) It is obtained by neutralizing with
For example, the primary amine salt type includes inorganic or organic acid salts of higher aliphatic amines (higher amines such as laurylamine, stearylamine, cetylamine, hardened tallow amine, and rosinamine); Examples include fatty acid (stearic acid, oleic acid, etc.) salts and the like.
Examples of the secondary amine salt type include inorganic acid salts or organic acid salts such as EO adducts of aliphatic amines.
Examples of the tertiary amine salt type include aliphatic amines (triethylamine, ethyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, etc.), aliphatic amine EO (2 mol or more). ) Adduct, alicyclic amine (N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine, 1,8-diazabicyclo (5,4,0) -7-undecene, etc.), Inorganic or organic acid salts of nitrogen-containing heterocyclic aromatic amines (4-dimethylaminopyridine, N-methylimidazole, 4,4′-dipyridyl, etc.); triethanolamine monostearate, stearamide ethyl diethylmethylethanolamine Inorganic acid salts or organic acid salts of tertiary amines such as

  The amphoteric surfactant (S-3) used in the present invention includes a carboxylate type amphoteric surfactant, a sulfate ester type amphoteric surfactant, a sulfonate type amphoteric surfactant, and a phosphate ester type amphoteric interface. Examples of the surfactant include amphoteric surfactants and amino acid-type amphoteric surfactants and betaine-type amphoteric surfactants.

Examples of carboxylate type amphoteric surfactants include amino acid type amphoteric surfactants, betaine type amphoteric surfactants, and imidazoline type amphoteric surfactants. Among these, amino acid type amphoteric surfactants are included in the molecule. Examples of amphoteric surfactants having an amino group and a carboxyl group include compounds represented by the following general formula.
_{[R-NH- (CH 2)} n-COO] mM
[Wherein R is 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. Etc. ]
Specifically, for example, an alkylaminopropionic acid type amphoteric surfactant (such as sodium stearylaminopropionate and sodium laurylaminopropionate); an alkylaminoacetic acid type amphoteric surfactant (such as sodium laurylaminoacetate) and the like can be mentioned. .

  Betaine-type amphoteric surfactants are amphoteric surfactants having a quaternary ammonium salt-type cation moiety and a carboxylic acid-type anion moiety in the molecule. For example, alkyldimethylbetaine (stearyl) represented by the following general formula: Dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, etc.), amide betaine (coconut oil fatty acid amide propyl betaine etc.), alkyl dihydroxyalkyl betaine (lauryl dihydroxyethyl betaine etc.) etc. are mentioned.

  Furthermore, examples of the imidazoline type amphoteric surfactant include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.

  Examples of other amphoteric surfactants include glycine-type amphoteric surfactants such as sodium lauroyl glycine, sodium lauryl diaminoethyl glycine, lauryl diaminoethyl glycine hydrochloride, dioctyl diaminoethyl glycine hydrochloride; pentadecylsulfotaurine and the like Examples include sulfobetaine-type amphoteric surfactants.

  Examples of the nonionic surfactant (S-4) include an AO addition type nonionic surfactant and a polyvalent alcohol type nonionic surfactant.

  The AO addition type nonionic surfactant is a higher fatty acid added to polyalkylene glycols obtained by adding AO directly to higher alcohol, higher fatty acid, alkylamine or the like, or by adding AO to glycols. Or AO is added to an esterified product obtained by reacting a higher alcohol with a polyhydric alcohol, or AO is added to a higher fatty acid amide.

Examples of AO include EO, PO, and BO.
Of these, EO and random or block adducts of EO and PO are preferred.
The number of moles of AO added is preferably 10 to 50 moles, and 50 to 100% by weight of the AO is preferably EO.

Specific examples of the AO addition type nonionic surfactant include oxyalkylene alkyl ethers (for example, octyl alcohol EO adduct, lauryl alcohol EO adduct, stearyl alcohol EO adduct, oleyl alcohol EO adduct, lauryl alcohol EO). PO block adducts, etc.); polyoxyalkylene higher fatty acid esters (for example, stearyl acid EO adduct, lauric acid EO adduct, etc.);
Polyoxyalkylene polyhydric alcohol higher fatty acid esters (eg, lauric acid diester of polyethylene glycol, oleic acid diester of polyethylene glycol, stearic acid diester of polyethylene glycol, etc.);
Polyoxyalkylene alkylphenyl ether (eg, nonylphenol EO adduct, nonylphenol EO / PO block adduct, octylphenol EO adduct, bisphenol A / EO adduct, dinonylphenol EO adduct, styrenated phenol EO adduct, etc.) Polyoxyalkylene alkylamino ethers (eg, laurylamine EO adducts, stearylamine EO adducts, etc.); polyoxyalkylene alkyl alkanolamides (eg, EO adducts of hydroxyethyl lauric acid amide, hydroxypropyl olein) EO adduct of acid amide, EO adduct of dihydroxyethyl lauric acid amide, etc.).

  Examples of the polyhydric alcohol type nonionic surfactant include polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid ester AO adducts, polyhydric alcohol alkyl ethers, and polyhydric alcohol alkyl ether AO adducts.

Specific examples of polyhydric alcohol fatty acid esters include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dioleate, sucrose monostearate, etc. Is mentioned.
Specific examples of polyhydric alcohol fatty acid ester AO adducts include ethylene glycol monooleate EO adduct, ethylene glycol monostearate EO adduct, trimethylolpropane monostearate EO / PO random adduct, sorbitan monolaurate EO addition Sorbitan monostearate EO adduct, sorbitan distearate EO adduct, sorbitan dilaurate EO / PO 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, lauryl glycoside and the like.
Specific examples of the polyhydric alcohol alkyl ether AO adduct include sorbitan monostearyl ether EO adduct, methyl glycoside EO / PO random adduct, lauryl glycoside EO adduct, stearyl glycoside EO / PO random adduct, and the like.

  Examples of the water-soluble polymer (T) include cellulosic compounds (eg, methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, and saponified products thereof), gelatin, starch, dextrin, gum arabic, and chitin. , Chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, in the sodium hydroxide part of polyacrylic acid) Sodium hydroxide, acrylic acid ester copolymer), styrene-maleic anhydride copolymer sodium hydroxide Beam (partial) neutralization product, water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.

The solvent (U) used in the present invention may be added to an aqueous medium as necessary during emulsification dispersion, or may be added to the emulsified dispersion [in the oil phase containing the resin (b)].
Specific examples of (U) include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, and cyclohexane ; Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene; esters such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate Or ester ether solvents; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl iso Ketone solvents such as tilketone, di-n-butylketone and cyclohexanone; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol; dimethyl Examples include amide solvents such as formamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide, heterocyclic compound solvents such as N-methylpyrrolidone, and mixed solvents of two or more of these.

The plasticizer (V) may be added to the aqueous medium as necessary during emulsification dispersion, or may be added to the dispersion to be emulsified [in the oily liquid (W)].
(V) is not limited at all, and the following are exemplified.
(V1) Phthalates [dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, etc.];
(V2) aliphatic dibasic acid ester [di-2-ethylhexyl adipate, 2-ethylhexyl sebacate, etc.];
(V3) trimellitic acid ester [tri-2-ethylhexyl trimellitic acid, trioctyl trimellitic acid, etc.];
(V4) Phosphate ester [triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.];
(V5) fatty acid ester [butyl oleate and the like];
(V6) and a mixture of two or more of these.

  The particle size of the resin particles (A) is usually smaller than the particle size of the resin particles (B), and from the viewpoint of particle size uniformity, the particle size ratio [volume average particle size of (A) / (B) The value of [volume average particle diameter] is preferably in the range of 0.001 to 0.3. The lower limit of the particle size ratio is more preferably 0.003, and the upper limit is more preferably 0.25. When the particle size ratio is larger than 0.3, (A) is not efficiently adsorbed on the surface of (B), so that the obtained particle size distribution of (C) tends to be wide.

The volume average particle size of the resin particles (A) can be appropriately adjusted within the above range of particle size ratios so as to be a particle size suitable for obtaining the resin particles (C) having a desired particle size.
The volume average particle diameter of (A) is generally preferably 0.0005 to 30 μm. The upper limit is more preferably 20 μm, particularly preferably 10 μm, and the lower limit is further preferably 0.01 μm, particularly preferably 0.02 μm, and most preferably 0.04 μm. However, for example, when it is desired to obtain (C) having a volume average particle diameter of 1 μm, preferably 0.0005 to 0.3 μm, particularly preferably in the range of 0.001 to 0.2 μm, and 10 μm of (C) is obtained. In the case of obtaining particles (C) of preferably 0.005 to 3 μm, particularly preferably 0.05 to 2 μm and 100 μm, preferably 0.05 to 30 μm, particularly preferably 0.1 to 20 μm. The volume average particle diameter can be measured with a laser type particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) or a Coulter counter [for example, trade name: Multitizer III (manufactured by Coulter)].

  In addition, since the said particle size ratio is easy to obtain, 0.1-300 micrometers is preferable as the volume average particle diameter of the resin particle (B) mentioned later. The upper limit is more preferably 250 μm, particularly preferably 200 μm, and the lower limit is more preferably 0.5 μm, particularly preferably 1 μm.

  As the resin (b) of the present invention, any resin can be used as well as the resin (a), and the same examples as in (a) can be used. (B) can be suitably selected depending on the application and purpose. In general, preferred as (b) are polyurethane resins, epoxy resins, vinyl resins, and polyester resins, and more preferred are vinyl resins, polyurethane resins, polyester resins, and combinations thereof.

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

In the production method of the present invention, the resin (b) or an organic solvent solution thereof is dispersed in the aqueous dispersion (W) of the resin particles (A) made of the resin (a), and the aqueous resin particles (A) are dispersed. An aqueous resin dispersion (X1) of resin particles (C) having a structure in which (A) is attached to the surface of (B) by forming resin particles (B) made of resin (b) in the dispersion. )
Alternatively, the precursor (b0) of the resin (b) or an organic solvent solution thereof is dispersed in the aqueous dispersion (W) of the resin particles (A) made of the resin (a), and the reaction of (b0) is further performed. Then, in the aqueous dispersion of the resin particles (A), the resin particles (B) made of the resin (b) are formed, whereby the resin particles having a structure in which (A) is attached to the surface of (B) An aqueous resin dispersion (X1) of (C) is obtained. Further, these two methods may be used in combination [for example, using a solvent solution of (b) and (b0)].

When dispersing the oily liquid (O) comprising at least one selected from the resin (b), the organic solvent solution of (b), the precursor (b0) of (b), and the organic solvent solution of (b0) A dispersion device can be used.
The dispersion apparatus used in the present invention is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. For example, a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer ( Batch type emulsifiers such as Special Machine Industries Co., Ltd., Ebara Milder (made by Aihara Seisakusho Co., Ltd.), TK Fill Mix, TK Pipeline Homo Mixer (made by Special Machine Industries Co., Ltd.), Colloid Mill (made by Shinko Pantech Co., Ltd.) ), Continuous emulsifiers such as slasher, trigonal wet pulverizer (Mitsui Miike Chemical Co., Ltd.), Captron (Eurotech Co., Ltd.), fine flow mill (Pacific Kiko Co., Ltd.), microfluidizer (Mizuho Kogyo Co., Ltd.) ), Nanomizer (manufactured by Nanomizer), APV Gaurin (manufactured by Gaurin), etc., membrane emulsifier (manufactured by Chilling Industries Co., Ltd.), etc. Membrane emulsification machine, Vibro Mixer (Hiyaka Kogyo) vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of homogenizing the particle diameter.

When the resin (b) is dispersed in the aqueous dispersion (W) of the resin particles (A), (b) is preferably a liquid. When (b) is solid at room temperature, it is dispersed in a liquid state at a temperature higher than the melting point, the organic solvent solution of (b) is used, the precursor (b0) of (b) or its organic A solvent solution may be used.
The viscosity of the oily liquid (O) comprising at least one selected from the resin (b), the organic solvent solution of (b), the precursor (b0) of the resin (b), and the organic solvent solution of (b0) From the viewpoint of diameter uniformity, the viscosity is usually preferably 10 to 50,000 mPa · s (measured with a B-type viscometer, temperature during dispersion), more preferably 100 to 10,000 mPa · s.
The temperature during 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 lowering the viscosity to the above preferred range by increasing the temperature.
The solvent used in the organic solvent solution (b) and the organic solvent solution (b0) is not particularly limited as long as it is a solvent that can dissolve (b) at room temperature or under heating. Specifically, the solvent (U) The same thing is illustrated. Although what is preferable differs depending on the type of (b), it is preferable that the SP value difference with (b) is 3 or less. Moreover, from the viewpoint of the particle size uniformity of the resin particles (C), a solvent that dissolves the resin (b) but hardly dissolves and swells the resin particles (A) made of the resin (a) is preferable.

In the production method of the present invention, an oily liquid (O) comprising at least one selected from the resin solution (b), the solvent solution of (b), the precursor (b0) of (b), and the solvent solution of (b0). It contains a tertiary amine (c) having a weight average molecular weight of 1000 or less as an essential component. When (c) has a molecular weight distribution, the weight average molecular weight of (c) (hereinafter referred to as Mw) is determined by gel permeation chromatography.
The Mw of (c) is preferably 900 or less, more preferably 800 or less, particularly preferably 700 or less, and most preferably 600 or less. When Mw exceeds 1000, the residual amount of (c) in the resin particles (C) increases, and the thermal characteristics (heat resistance, melt viscosity, etc.) and electrical characteristics of (C) deteriorate.
The number of carbon atoms in (c) is preferably 3-25. The lower limit is more preferably 4, more preferably 5, particularly preferably 6, and most preferably 7. The upper limit is more preferably 23, still more preferably 22, particularly preferably 21, and most preferably 20. When the amount is not less than the above range, the residual amount of (c) in the resin particles (C) decreases, and the thermal characteristics (heat resistance, melt viscosity, etc.) and electrical characteristics of (C) become better.

Specific examples of the tertiary amine (c) are not particularly limited as long as they are within the above molecular weight range, but are aliphatic amines having 3 to 25 carbon atoms, heterocyclic amines having 3 to 25 carbon atoms, and carbon numbers. 6-25 aromatic amines etc. are mentioned, You may use 2 or more types together.
Examples of the aliphatic amine having 3 to 25 carbon atoms include N-methyldiethylamine, N, N-dimethylisopropylamine, tri-n-ethylamine, tri-n-butylamine, tri-n-hexylamine, N, N-diethylcyclohexyl. Examples include amines, N, N-diethylbutylamine, N, N-dimethyloctylamine, N, N-dimethylpropargylamine and the like. Examples of the heterocyclic amine having 3 to 25 carbon atoms include 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undecene-7, and bis (2-morpholinoethyl). Examples include ether. Examples of the aromatic amine having 6 to 25 carbon atoms include N, N-dimethylbenzylamine. Among these, aliphatic amines and heterocyclic amines having 3 to 25 carbon atoms are preferable, and triethylamine, 1,8-diazabicyclo [5,4,0] undecene-7, and bis ( 2-morpholinoethyl) ether, particularly preferably 1,8-diazabicyclo [5,4,0] undecene-7 and bis (2-morpholinoethyl) ether.

In the production method of the present invention, the acid value and the total amine value of the oily liquid (O) are 1 to 50 (mg KOH / g, and the following acid value and amine value are the same). Moreover, the tertiary amine value of (O) is 0.1-50.
The lower limit of the acid value of (O) is preferably 2, more preferably 3, particularly preferably 4, most preferably 5, and the upper limit is preferably 45, more preferably 40, particularly preferably 35, most preferably Preferably it is 30. The lower limit of the total amine value is preferably 2, more preferably 3, particularly preferably 4, and the upper limit is preferably 45, more preferably 40, particularly preferably 35, most preferably 30. The lower limit of the tertiary amine value is preferably 0.5, more preferably 1, particularly preferably 2, most preferably 3, and the upper limit is preferably 45, more preferably 40, particularly preferably 35, most preferably Preferably it is 30.
By setting the acid value, total amine value, and tertiary amine value within the above ranges, the acid present in (O) when (O) is dispersed in the aqueous dispersion (W) of resin particles (A) Due to the amphiphilic nature of the amine salt, (O) exhibits self-emulsifying properties and is readily dispersed in water. Therefore, when any of the acid value, total amine value, and tertiary amine value is outside the above range, it becomes difficult to stably disperse (O) in (W).

Further, the absolute value of the difference between the acid value of (O) and the total amine value is preferably 10 or less, more preferably 9.5 or less, particularly preferably 9 or less, and most preferably 8.5 or less. If it is 10 or less, the resin particles (A) can be easily adsorbed to the resin particles (B), and an effect of preventing coalescence of the resin particles (C) can be obtained. Is easy to obtain.
For the same reason, the [acid value / total amine value] is preferably 0.2 to 5. The lower limit is more preferably 0.22, more preferably 0.25, particularly preferably 0.29, most preferably 0.33, and the upper limit is more preferably 4.5, still more preferably 4, particularly preferably. Is 3.5, most preferably 3.

In the present invention, the acid value, total amine value, and tertiary amine value are measured as follows. In addition, the solvent used below is a preferable example. When it is difficult to dissolve with the following solvents, the sample may be appropriately changed to a soluble solvent and measured.
[Acid value]
1 g of a sample is dissolved in 100 ml of a toluene / acetone / methanol mixed solvent (75: 12.5: 12.5), titrated with a 1/10 N potassium hydroxide / methanol solution, and an acid value is calculated from the following formula.
Acid value = 5.61 × (drop amount [mg]) × (potency of drop solution) / (sample weight [g])
[Total amine value]
1 g of sample is dissolved in 50 ml of dimethylformamide, titrated with a 1 / 100N hydrochloric acid / methanol solution, and the total amine value is calculated from the following formula.
Total amine number = 0.561 × (drop amount [mg]) × (potency of dripping solution) / (sample weight [g])
[Tertiary amine value]
1 g of sample is dissolved in 50 ml of dimethylformamide, 20 ml of a mixed solution of acetic anhydride / acetic acid (weight ratio 9: 1) is added and left at room temperature for 3 hours. Add 30 ml of acetic acid and titrate with 0.1N perchloric acid / acetic acid solution. At the same time, blank measurement is performed, and the tertiary amine value is calculated from the following formula.
Tertiary amine value = 0.561 × {(sample drop amount [mg]) − (blank drop amount [mg])} × (titer of drop solution) / (sample weight [g])

  The means for adjusting the acid value of (O) may be any means. In addition to the method using the resin (b) or (b0) whose acid value is in the above range, acetic acid, having 3 to 24 carbon atoms. You may use the method of adding low molecular organic acids, such as a fatty acid, in (O), and the method of adding inorganic acids, such as hydrochloric acid, phosphoric acid, and oxalic acid. As said organic acid, what melt | dissolves and compatibilizes uniformly in (O) is preferable.

In the present invention, the total amine value, the absolute value of the difference between the acid value and the total amine value, and [acid value / total amine value] can be adjusted with any amine such as the polyamine (16) described above. It is preferable to adjust according to the addition amount of the tertiary amine (c).
(C) is a case where, as (b) or (b0), for example, when a compound containing a functional group reactive with active hydrogen such as an isocyanate group or an epoxy group is used, the above all amines are not accompanied by side reactions. In addition, the catalytic effect can be obtained in the reaction (b0). In addition, since (c) has stable chemical characteristics, an appropriate amount can be left in the resin particles (C) by selecting a tertiary amine structure. The surface properties (hydrophilicity, lipophilicity, electrical properties, etc.) can be controlled.

The residual amount of the tertiary amine (c) in the resin particles (C) is usually 10 to 500 ppm. The lower limit is preferably 12 ppm, more preferably 15 ppm, particularly preferably 30 ppm, and the upper limit is preferably 450 ppm, more preferably 400 ppm, particularly preferably 350 ppm, and most preferably 300 ppm. If it is out of the above range, the thermal characteristics (heat resistance, melt viscosity, etc.) and electrical characteristics of (C) are lowered.
The residual amount of (c) in the resin particles (C) can be obtained by a method in which (C) is dissolved in a solvent and a tertiary amine value is measured by the above-mentioned method, or quantitative determination by a gas chromatograph.

The measurement conditions of (c) by the gas chromatograph in the present invention are as follows.
Model: Shimadzu GC2010
Column: DB-5 (5% phenylmethylpolysiloxane, inner diameter 0.25 mm,
30m long)
Eluent: Dimethylformamide Flow rate: 40.5 ml / min
Detector temperature: 250 ° C
Injection volume: 1 μl

  The residual amount of (c) in (C) varies depending on the type of (c), and can be controlled by devolatilization and washing operations after granulation. For example, when it is desired to keep the residual amount of (c) low, triethylamine having a low boiling point or triethanolamine having a high SP value is effective. In order to enhance the function of the resin particles (C) or to enhance the effect of (b0) as a reaction catalyst, when it is desired to increase (c) in (C), on the contrary, a high boiling point, low SP value tertiary class. Amines are effective.

  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, (b0) Includes the above-mentioned vinyl monomers (which may be used alone or mixed) and solvent solutions thereof, and the resin (b) is a condensation resin (for example, polyurethane resin, epoxy resin, polyester resin). ), (B0) is exemplified by a combination of a prepolymer (α) having a reactive group and a curing agent (β).

  When a vinyl monomer is used as the precursor (b0), the method of reacting the precursor (b0) to obtain a resin (b) includes, for example, an oil-soluble initiator, monomers, and optionally a solvent (U). An oil phase comprising a method of dispersing and suspending the resulting oil phase in water in the presence of a water-soluble polymer (T) and performing a radical polymerization reaction by heating (so-called suspension polymerization method), monomers and, if necessary, a solvent (U) Is emulsified in an aqueous dispersion of resin particles (A) containing an emulsifier (same as the surfactant (S)) and a water-soluble initiator (so-called radical polymerization reaction) Emulsion polymerization method) and the like.

  Examples of the oil-soluble or water-soluble initiator include peroxide-based polymerization initiator (I) and azo-based polymerization initiator (II). Further, the redox polymerization initiator (III) may be formed by using a peroxide polymerization initiator (I) and a reducing agent in combination. Furthermore, you may use 2 or more types together from (I)-(III).

(I) As the peroxide polymerization initiator, (I-1) oil-soluble peroxide polymerization initiator: acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxy Dicarbonate, 2,4-dichlorobenzoyl peroxide, t-butyl peroxybivalate, 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, parachlorobenzoy 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-dit-butyl Peroxyhexane, t-butyl cumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, pinane hydroperoxide Kisaido, 2,5-dimethyl-2,5-dihydro peroxide, cumene peroxide and the like (I-2) water-soluble peroxide polymerization initiators: hydrogen peroxide, peracetic acid, ammonium persulfate, sodium persulfate, etc.

(II) Azo polymerization initiator:
(II-1) Oil-soluble azo polymerization initiator: 2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexane 1-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-dimethylvaleronitrile), etc. (II-2) Water-soluble azo polymerization initiator: azobisamidinopropane salt, azobiscyanovaleric Acid (salt), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], etc.

(III) Redox polymerization initiator (III-1) Non-aqueous redox polymerization initiator: oil-soluble peroxide such as hydroperoxide, dialkyl peroxide, diacyl peroxide, tertiary amine, naphthenic acid salt, mercaptans In combination with oil-soluble reducing agents such as organometallic compounds (triethylaluminum, triethylboron, diethylzinc, etc.) (III-2) Water-based redox polymerization initiators: Examples thereof include a combination of a peroxide and a water-soluble inorganic or organic reducing agent (divalent iron salt, sodium hydrogen sulfite, alcohol, polyamine, etc.).

  As the precursor (b0), a combination of a prepolymer (α) having a reactive group and a curing agent (β) can also be used. Here, “reactive group” means a group capable of reacting with the curing agent (β). In this case, as a method for forming the resin (b) by reacting the precursor (b0), an oil phase containing a reactive group-containing prepolymer (α) and a curing agent (β) and, if necessary, a solvent (U) is used. The resin particles (A) are dispersed in an aqueous dispersion, and the reactive group-containing prepolymer (α) and the curing agent (β) are reacted by heating to form resin particles (B) made of the resin (b). Method: 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 obtain resin (b). A method of forming resin particles (B) comprising: a reactive group-containing prepolymer (α) or a solvent solution thereof as a resin when the reactive group-containing prepolymer (α) is cured by reacting with water. Reacted with water by dispersing it in an aqueous dispersion of particles (A) And a method of forming the resin particles (B) made 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 [1] and [2].
[1]: 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). There is a combination.
[2]: The reactive group of the reactive group-containing prepolymer (α) is an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) that can react with the active hydrogen-containing group. combination.
Among these, [1] is more preferable from the viewpoint of the reaction rate in water.
In the combination [1], examples of the functional group (α1) capable of reacting with the active hydrogen compound include an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (α1d), and And acid halide groups (α1e). Among these, (α1a), (α1b) and (α1c) are preferable, and (α1a) and (α1b) are particularly preferable.
The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent.
Examples of the blocking agent include oximes [acetooxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; lactams [γ-butyrolactam, ε-caprolactam, γ-valerolactam Etc.]; C1-C20 aliphatic alcohols [ethanol, methanol, octanol, etc.]; Phenols [phenol, m-cresol, xylenol, nonylphenol, etc.]; Active methylene compounds [acetylacetone, ethyl malonate, ethyl acetoacetate, etc.] Etc.]; basic nitrogen-containing compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.]; and mixtures of two or more thereof That.
Of these, oximes are preferred, and methyl ethyl ketoxime is particularly preferred.

Examples of the skeleton of the reactive group-containing prepolymer (α) include polyether (αw), polyester (αx), epoxy resin (αy), and polyurethane (αz). Of these, (αx), (αy) and (αz) are preferred, and (αx) and (αz) are particularly preferred.
Examples of the polyether (αw) include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, and the like.
Examples of polyester (αx) include polycondensates of diol (11) and dicarboxylic acid (13), polylactones (ring-opening polymerization products of ε-caprolactone), and the like.
Examples of the epoxy resin (αy) include addition condensation products of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S) and epichlorohydrin.
Examples of polyurethane (αz) include polyaddition product of diol (11) and polyisocyanate (15), polyaddition product of polyester (αx) and polyisocyanate (15), and the like.

As a method of adding a reactive group to polyester (αx), epoxy resin (αy), polyurethane (αz), etc.,
[1]: A method of leaving a functional group of a constituent component at the terminal by excessively using one of two or more constituent components,
[2]: The functional group of the constituent component is left at the terminal by using one of two or more constituent components in excess, and further contains a functional group and a reactive group capable of reacting with the remaining functional group. Examples include a method of reacting a compound.
In the above method [1], a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, an isocyanate A group-containing polyurethane 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 polyol (1) to polycarboxylic acid (2) is equivalent ratio [OH] / [COOH of hydroxyl group [OH] to carboxyl group [COOH]. ] Is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.3 / 1 to 1.02 / 1. In the case of other skeletons and end group prepolymers, the ratios are the same except that the constituent components are changed.
In the above method [2], an isocyanate group-containing prepolymer is obtained by reacting the preprimer obtained in the above method [1] with a polyisocyanate, and a blocked polyisocyanate is reacted to cause a blocked isocyanate group-containing prepolymer. A polymer is obtained, an epoxy group-containing prepolymer is obtained by reacting polyepoxide, and an acid anhydride group-containing prepolymer is obtained by reacting polyanhydride.
The amount of the compound containing a functional group and a reactive group is, for example, when the isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate, and the ratio of the polyisocyanate is an isocyanate group [NCO]. The equivalent ratio [NCO] / [OH] of the hydroxyl group [OH] of the hydroxyl group-containing polyester is usually 5/1 to 1/1, preferably 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1. 1.5 / 1. In the case of prepolymers having other skeletons and 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 on average. It is a piece. By setting it as the above range, the molecular weight of the cured product obtained by reacting with the curing agent (β) is increased.
The Mn of the reactive group-containing prepolymer (α) is usually 500 to 30,000, preferably 1,000 to 20,000, and more preferably 2,000 to 10,000.
The Mw of the reactive group-containing prepolymer (α) is 1,000 to 50,000, preferably 2,000 to 40,000, more preferably 4,000 to 20,000.
The viscosity of the reactive group-containing prepolymer (α) is usually not more than 2,000 poise, preferably not more than 1,000 poise at 100 ° C. By setting it to 2,000 poise or less, it is preferable in that resin particles (C) having a sharp particle size distribution can be obtained with a small amount of solvent.

Examples of the active hydrogen group-containing compound (β1) include polyamine (β1a), polyol (β1b), polymercaptan (β1c) and water (β1d) which may be blocked with a detachable compound. Among these, preferred are (β1a), (β1b) and (β1d), more preferred are (β1a) and (β1d), and particularly preferred are blocked polyamines and (β1d ).
(Β1a) is exemplified by those similar to polyamine (16). Preferred as (β1a) are 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine and mixtures thereof.

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

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

If necessary, a reaction terminator (βs) can be used together with the active hydrogen group-containing compound (β1). By using a reaction terminator in combination with (β1) at a certain ratio, it is possible to adjust (b) to a predetermined molecular weight.
As the reaction terminator (βs), monoamine (diethylamine, dibutylamine, butylamine, laurylamine, monoethanolamine, diethanolamine, etc.);
Monoamine blocked (ketimine compound etc.);
Monool (methanol, ethanol, isopropanol, butanol, phenol;
Monomercaptan (such as butyl mercaptan, lauryl mercaptan);
Monoisocyanates (such as lauryl isocyanate, phenyl isocyanate);
Monoepoxide (such as butyl glycidyl ether) can be used.

As the active hydrogen-containing group (α2) of the reactive group-containing prepolymer (α) in the combination [2], an amino group (α2a), a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), a mercapto group ( α2c), a carboxyl group (α2d), and an organic group (α2e) blocked with a compound from which they can be removed. Of these, (α2a), (α2b) and an organic group (α2e) blocked with a compound capable of removing an amino group are preferred, and (α2b) is particularly preferred.
Examples of the organic group blocked with the compound from which the amino group can be removed include the same groups as in the case of (β1a).

  Examples of the compound (β2) capable of reacting with the active hydrogen-containing group include polyisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polyanhydride (β2d), and polyacid halide (β2e). It is done. Of these, (β2a) and (β2b) are preferable, and (β2a) is more preferable.

Examples of the polyisocyanate (β2a) include those similar to the polyisocyanate (15), and preferred ones are also the same.
Examples of the polyepoxide (β2b) are the same as those of the polyepoxide (18), and preferred ones are also the same.

Examples of the polycarboxylic acid (β2c) include dicarboxylic acid (β2c-1) and trivalent or higher polycarboxylic acid (β2c-2), (β2c-1) alone, and (β2c-1) and a small amount of ( A mixture of β2c-2) is preferred.
Examples of the dicarboxylic acid (β2c-1) include the dicarboxylic acid (13), and examples of the polycarboxylic acid include those similar to the polycarboxylic acid (5), and preferable ones 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).
Furthermore, a reaction terminator (βs) can be used together with (β2) if necessary.

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

  Resin (b) obtained by reacting a precursor (b0) comprising a reactive group-containing prepolymer (α) and a curing agent (β) in an aqueous medium is a constituent of resin particles (B) and resin particles (C). Become. The Mw of the resin (b) obtained by reacting (α) and (β) is usually 3,000 or more, preferably 3,000 to 10,000,000, more preferably 5,000 to 1,000,000.

  Also, a polymer that does not react with (α) and (β) [so-called dead polymer] is included in the system when the reactive group-containing prepolymer (α) and the curing agent (β) react in an aqueous medium. You can also. In this case, (b) is a mixture of a resin obtained by reacting (α) and (β) in an aqueous medium and a resin not reacted.

Other additives (pigments, fillers, antistatic agents, colorants, release agents, charge control agents, ultraviolet absorbers, antioxidants, blocking agents in the resin (a) and / or resin (b) of the present invention Inhibitors, heat stabilizers, flame retardants, etc.) may be mixed. As a method of adding other additives in (a) or (b), the aqueous resin dispersion may be mixed in an aqueous medium, but (a) or (b) and the additive may be added in advance. More preferably, after mixing, the mixture is added and dispersed in an aqueous medium.
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 can be added by a known dyeing method, or the additive can be impregnated with the solvent (U) and / or the plasticizer (V). .

  The usage-amount of the aqueous medium with respect to 100 parts of resin (b) is 50-2,000 weight part normally, Preferably it is 100-1,000 weight part. When it is 50 parts by weight or more, the dispersed state of (b) is good. It is economical that it is 2,000 parts by weight or less.

The elongation and / or crosslinking reaction time is selected depending on the reactivity of the reactive group structure of the prepolymer (α) and the combination of the curing agent (β), preferably 10 minutes to 40 hours, more preferably 30. Min to 24 hours.
The reaction temperature is usually 0 to 150 ° C., preferably 50 to 120 ° C.
Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate in the case of a reaction between an isocyanate and an active hydrogen compound.

Resin particles (C) are prepared by adding resin (b), a solvent solution of resin (b), a precursor (b0) of resin (b) in an aqueous dispersion (W) of resin particles (A) made of resin (a). ) Or a solvent solution of the precursor (b0), and in the case of the precursor (b0), the precursor (b0) is reacted to form the resin (b), and the resin particles ( After forming the aqueous resin dispersion (X1) of the resin particles (C) having a structure in which the resin particles (A) adhere to the surface of B), the aqueous medium is removed from the aqueous resin dispersion (X1). Is obtained. As a method of removing the aqueous medium,
[1] A method of drying (X1) under reduced pressure or normal pressure [2] A method of solid-liquid separation with a centrifuge, spacula filter, filter press, etc., and drying the resulting powder [3] (X1) Method of freezing and drying (so-called freeze drying)
Etc. are exemplified.
In the above [1] and [2], when the obtained powder is dried, it can be performed using a known facility such as a fluidized bed dryer, a vacuum dryer, or a circulating dryer.
Moreover, it can classify | classify using a wind classifier etc. as needed, and can also be set as predetermined particle size distribution.

  The resin particles (C) are substantially composed of small resin particles (A) and large resin particles (B), and (A) is present in a form attached to the surface of (B). When it is desired to increase the adhesion of both particles, when dispersed in an aqueous medium, (A) and (B) have positive and negative charges, or (A) and (B) have the same charge. In the case of having a surfactant (S) or a water-soluble polymer (T), those having a charge opposite to (A) and (B) are used, or the SP values of the resins (a) and (b). It is effective to make the difference 2 or less.

  From the viewpoints of particle size uniformity, storage stability and the like of the resin particles (C), (C) consists of 0.1 to 50% by weight of (A) and 50 to 99.9% by weight of (B). It is more preferable that it consists of 0.2 to 40% by weight of (A) and 60 to 99.8% by weight of (B).

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

From the viewpoint of particle size uniformity, the coefficient of variation of the volume distribution of the resin particles (C) is preferably 30% or less, and more preferably 0.1 to 15%. Moreover, from the uniformity of the particle diameter, the [volume average particle diameter / number average particle diameter] of the resin particles (C) is preferably 1.0 to 1.5, and preferably 1.0 to 1.45. Is more preferable.
The volume average particle size of (C) varies depending on the application, but is generally preferably 0.1 to 300 μm. The upper limit is more preferably 250 μm, particularly preferably 200 μm, and the lower limit is more preferably 0.5 μm, particularly preferably 1 μm.
The volume average particle diameter and the number average particle diameter can be simultaneously measured with a Coulter counter.

The resin particle (C) of the present invention gives desired irregularities to the particle surface by changing the particle size of the resin particle (A) and the resin particle (B) and the coverage of the (B) surface by (A). can do. When it is desired to improve the powder fluidity, the BET specific surface area of (C) is preferably 0.5 to 5.0 m ² / g. The BET specific surface area can be measured (measurement gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen) using a specific surface area meter such as QUANTASORB (manufactured by Yuasa Ionics).
Similarly, from the viewpoint of powder fluidity, the surface average center line roughness Ra of (C) is preferably 0.01 to 0.8 μm. Ra is a value obtained by arithmetically averaging the absolute value of the deviation between the roughness curve and its center line, and can be measured by, for example, a scanning probe microscope system (manufactured by Toyo Technica).

  The shape of the resin particles (C) is preferably spherical from the viewpoint of powder flowability, melt leveling properties and the like. In that case, it is preferable that the particles (A) and the particles (B) are also spherical. In (C), Wadell's practical sphericity is preferably 0.85 to 1.00. The Wadell practical sphericity is obtained from a ratio of a diameter of a circle having an area equal to the projected area of the particle and a diameter of a circle having a minimum area circumscribing the projected image of the particle. The projected image of the particles can be taken with, for example, a scanning electron microscope (SEM).

The aqueous resin dispersion (X2) of the resin particles (B) is obtained by removing the resin particles (A) and the resin particles (B) adhering to each other in the aqueous resin dispersion (X1), and It can be obtained by separating and removing (A) from the resin dispersion or by dissolving (A) in (X1) without dissolving (B). The dissolved material (A) may be separated and removed as necessary.
Furthermore, resin particles (B) are obtained by removing the aqueous medium from the aqueous resin dispersion (X2). Examples of the method for removing the aqueous medium include the same method as in the case of the resin particles (C).
In the aqueous resin dispersion (X1), as a method of detaching the adhering resin particles (A) and resin particles (B),
[1] Method of ultrasonically treating (X1) [2] Method of diluting (X1) with a large amount of water or a water-soluble organic solvent such as methanol, ethanol or acetone, and applying shear by stirring [3] (X1 Method [4] (X1) in which acid, alkali, inorganic salt or the like is added to the mixture, and shear is applied by stirring, and shearing is applied by stirring [5] (X1) contains a solvent [resin (a )) And / or resin (b) when the solvent solution is dispersed in the aqueous medium or when the solvent is dissolved in the aqueous medium], a method for removing the solvent is exemplified.

As a method for dissolving the resin particles (A) in the aqueous resin dispersion (X1),
[1] When the resin (a) is a resin having an acidic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group (generally, the molecular weight per acidic functional group is preferably 1,000 or less) And a method of adding an alkali such as sodium hydroxide, potassium hydroxide, ammonia, DBU or an aqueous solution thereof to the aqueous resin dispersion (X1) [2] The resin (a) is a primary amino group, a secondary amino group, When the resin has a basic functional group such as a tertiary amino group or a quaternary ammonium base (generally, the molecular weight per basic functional group is preferably 1,000 or less), an aqueous resin dispersion ( A method of adding an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid or an aqueous solution thereof into X1) [3] When resin (a) is dissolved in a specific solvent (U) {generally resin (a) and solvent ( U) SP value difference Is preferably 2.5 or less}, a method of adding a specific solvent (U) to the aqueous resin dispersion (X1) is exemplified.

As a method for separating and removing the resin particles (A) or a dissolved product thereof from the aqueous resin dispersion,
[1] A method of filtering using a filter paper, a filter cloth, a mesh, etc. having a certain opening, and filtering out only the resin particles (B) [2] Only the resin particles (B) are sedimented by centrifugation, and the supernatant Examples thereof include a method of removing the resin particles (A) contained therein or a dissolved product thereof.

The resin particles (B) of the present invention have a particle size ratio of the resin particles (A) to the resin particles (B), and a coverage of the surface (B) by (A) in the aqueous resin dispersion (X1), ( The surface of the particle can be made smooth by changing the depth of (A) embedded in (B) on the (B) / aqueous medium interface in X1), or desired irregularities can be given to the particle surface. can do.
The (B) surface coverage by (A) and the depth at which (A) is embedded on the (B) side can be controlled by the following method.
[1] When (X1) is manufactured, if (A) and (B) have positive and negative charges, the coverage and depth increase. In this case, the coverage and the depth increase as the charges in (A) and (B) are increased.
[2] When manufacturing (X1), if (A) and (B) have charges of the same polarity (both positive or both negative), the coverage is lowered and the depth is reduced. There is a tendency. In this case, in general, the use of the active agent (S) and / or the water-soluble polymer (T) [particularly those having a reverse charge to (A) and (B)] increases the coverage. Moreover, when using water-soluble polymer (T), depth becomes small, so that the molecular weight of water-soluble polymer (T) is large.
[3] When (X1) is produced, the resin (a) has an acidic functional group such as a carboxyl group, a phosphoric acid group, and a sulfonic acid group (generally, the molecular weight per acidic functional group is 1,000 or less) In other words, the lower the pH of the aqueous medium, the greater the coverage and depth. Conversely, the higher the pH, the smaller the coverage and depth.
[4] When producing (X1), the resin (a) has a basic functional group such as a primary amino group, a secondary amino group, a tertiary amino group, or 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 depth.
[5] The coverage and depth increase as the SP value difference between the resin (a) and the resin (b) decreases.

  The volume average particle size of the obtained resin particles (B) varies depending on the intended use, but is generally preferably 0.1 to 300 μm. The upper limit is more preferably 250 μm, particularly preferably 200 μm, and the lower limit is more preferably 0.5 μm, particularly preferably 1 μm. In addition, from the particle size uniformity, the [volume average particle size / number average particle size] of (B) is preferably 1.0 to 1.5, and more preferably 1.0 to 1.45.

The residual amount of the tertiary amine (c) in the resin particles (B) is usually 10 to 500 ppm.
The lower limit is preferably 12 ppm, more preferably 15 ppm, particularly preferably 30 ppm, and the upper limit is preferably 450 ppm, more preferably 400 ppm, particularly preferably 350 ppm, and most preferably 300 ppm. When it is out of the above range, the thermal characteristics (heat resistance, melt viscosity, etc.) and electrical characteristics of (B) are deteriorated.
The remaining amount of (c) in (B) can be determined by the method described above. Further, the remaining amount of (c) in (B) can be controlled by the same method as in (C).

In order to improve the powder fluidity, the BET specific surface area of the resin particles (B) is preferably 0.5 to 5.0 m ² / g, and the surface average center line roughness Ra is 0.01. It is preferable that it is -0.8 micrometer.
The shape of the resin particles (B) is preferably spherical from the viewpoint of powder flowability, melt leveling properties, etc., and Wadell's practical sphericity is preferably 0.85 to 1.00, more preferably. 0.90 to 1.00.

  Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto. In the following description, “parts” means parts by weight and “%” means% by weight.

<Production Example 1>
Into a reaction vessel equipped with a stirrer and a dehydrator, 218 parts of bisphenol A / EO 2 mol adduct, 537 parts of bisphenol A / PO 3 mol adduct, 213 parts of terephthalic acid, 47 parts of adipic acid and 2 parts of dibutyltin oxide are added. Then, after dehydration reaction at 230 ° C. under normal pressure for 5 hours, dehydration reaction was performed under reduced pressure of 3 mmHg for 5 hours. The mixture was further cooled to 180 ° C., 43 parts of trimellitic anhydride was added, and the reaction was performed at normal pressure for 2 hours to obtain [Polyester Resin 1]. [Polyester resin 1] had a Tg of 44 ° C., Mn of 2700, Mw of 6500, and an acid value of 25.

<Production Example 2>
In a reaction vessel equipped with a stirrer and a dehydrator, 681 parts of bisphenol A / EO 2 molar adduct, 81 parts of bisphenol A / PO2 molar adduct, 275 parts of terephthalic acid, 7 parts of adipic acid, 22 parts of trimellitic anhydride, dibutyl 2 parts of tin oxide was added, and after 5 hours of dehydration reaction at 230 ° C. under normal pressure, 5 hours of dehydration reaction was performed under reduced pressure of 3 mmHg to obtain [Polyester Resin 2]. [Polyester resin 2] had a Tg of 54 ° C., Mn of 2200, Mw of 9500, an acid value of 0.8, and a hydroxyl value of 53.

<Production Example 3>
In an autoclave, 407 parts of [Polyester resin 2] obtained in Production Example 2, 54 parts of IPDI, and 485 parts of ethyl acetate are charged, and the reaction is carried out in a sealed state at 100 ° C. for 5 hours. A prepolymer solution 1] was obtained. [Nurethane Prepolymer Solution 1] had an NCO content of 0.8%.

<Production Example 4>
A reaction vessel equipped with a stirrer, a solvent removal device, and a thermometer was charged with 50 parts of isophoronediamine and 300 parts of methyl ethyl ketone, reacted at 50 ° C. for 5 hours, and then desolvated to form a ketimine compound [curing Agent 1] was obtained. The total amine value of [Curing Agent 1] was 415.

<Production Example 5>
In a reaction vessel equipped with a stirring bar and a thermometer, water 683 parts, sodium salt of methacrylic acid EO adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 139 parts of styrene, 138 parts of methacrylic acid, When 184 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to disperse the aqueous resin of vinyl resin (styrene salt copolymer of styrene / methacrylic acid / butyl methacrylate / methacrylic acid EO adduct). A liquid [fine particle dispersion] was obtained. The volume average particle diameter of the [fine particle dispersion 1] measured by LA-920 was 0.15 μm.

<Production Example 6>
955 parts of water, 15 parts of [Fine Particle Dispersion 1] obtained in Production Example 5 and 30 parts of sodium dodecyl diphenyl ether disulfonate solution (Eleminol MON7, manufactured by Sanyo Chemical Industries) are put into a container equipped with a stir bar and milky white Liquid [aqueous phase 1] was obtained.

<Production Example 7>
[Aqueous Phase 2] was obtained in the same manner as in <Production Example 6> except that 15 parts of [Fine Particle Dispersion 1] were not added.

<Example 1>
Into a beaker, 177 parts of [Polyester resin 1], 181 parts of ethyl acetate, 39.2 parts of [Urethane prepolymer solution 1], 0.9 part of [Curing agent 1] and 2.8 parts of triethylamine were dissolved and dissolved. The mixture was homogenized to obtain [Resin Solution 1]. The acid value of [resin solution 1] is 11.0, the total amine value is 4.8, the tertiary amine value is 3.8, and the absolute value of the difference between the acid value and the total amine value is 6.2. / Total amine number] was 2.3. In this [resin solution 1], 600 parts of [aqueous phase 1] are added, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) is used. The solvent was removed with an evaporator at a reduced pressure of −0.05 MPa (gauge pressure), a temperature of 40 ° C., and a rotation speed of 100 rpm for 30 minutes to obtain an aqueous resin dispersion (D1).
(D1) Centrifugation of 100 parts, addition of 60 parts of water, centrifugation and solid-liquid separation were repeated twice, followed by drying at 35 ° C. for 1 hour to obtain resin particles (P1). The characteristic values of (P1) are shown in Table 1.

<Example 2>
In the above <Example 1>, [resin solution 2] was obtained by the same method using bis (2-morpholinoethyl) ether instead of triethylamine. The acid value of [resin solution 2] is 11.0, the total amine value is 4.1, the tertiary amine value is 3.2, the absolute value of the difference between the acid value and the total amine value is 6.9, [acid value / Total amine number] was 2.7. Further, an aqueous resin dispersion (D2) and resin particles (P2) were obtained in the same manner. The characteristic values of (P2) are shown in Table 1.

<Example 3>
In <Example 1> above, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) was used instead of triethylamine, and [Resin Solution 3] was obtained in the same manner. The acid value of [resin solution 3] is 11.0, the total amine value is 6.0, the tertiary amine value is 5.1, the absolute value of the difference between the acid value and the total amine value is 5.0, [acid value / Total amine number] was 1.8. Further, an aqueous resin dispersion (D3) and resin particles (P3) were obtained in the same manner. The characteristic values of (P3) are shown in Table 1.

<Example 4>
In a beaker, 195 parts of [Polyester resin 1], 200 parts of ethyl acetate, and 4.9 parts of triethylamine were added and dissolved and mixed to obtain [Resin solution 4]. The acid value of [resin solution 4] is 12.2, the total amine value is 6.8, the tertiary amine value is 6.8, and the absolute value of the difference between the acid value and the total amine value is 5.4, [acid value] / Total amine number] was 1.8. In this [resin solution 4], 600 parts of [Aqueous phase 1] are added, a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) is used, a dispersion operation is performed at 25 ° C. for 1 minute at a rotational speed of 12000 rpm, and a film The solvent was removed with an evaporator at a reduced pressure of -0.05 MPa (gauge pressure), a temperature of 40 ° C., and a rotation speed of 100 rpm for 30 minutes to obtain an aqueous resin dispersion (D4).
(D4) Centrifugating 100 parts, adding 60 parts of water, centrifuging and solid-liquid separation was repeated twice, followed by drying at 35 ° C. for 1 hour to obtain resin particles (P4). The characteristic values of (P4) are shown in Table 1.

<Example 5>
Into a beaker, 387 parts of [urethane prepolymer 1], 7 parts of ethyl acetate, 3.9 parts of acetic acid, and 2.9 parts of triethylamine were added and dissolved and mixed to obtain [resin solution 5]. The acid value of [resin solution 5] is 9.0, the total amine value is 4.0, the tertiary amine value is 4.0, and the absolute value of the difference between the acid value and the total amine value is 5.0. / Total amine number] was 2.3. In this [resin solution 5], 600 parts of [aqueous phase 1] are added, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) is used. The solvent was removed with an evaporator at a reduced pressure of −0.05 MPa (gauge pressure), a temperature of 40 ° C., and a rotation speed of 100 rpm for 30 minutes to obtain an aqueous resin dispersion (D5).
(D5) Centrifugating 100 parts, adding 60 parts of water, centrifuging and solid-liquid separation was repeated twice, and then dried at 35 ° C. for 1 hour to obtain resin particles (P5). Table 1 shows the characteristic values of (P5).

<Example 6>
To the aqueous resin dispersion (D5) obtained in the above <Example 5>, several drops of 5% aqueous sodium hydroxide solution are added, the pH of the slurry is set to 12, and 13, The mixture was stirred at 000 rpm for 10 minutes to obtain an aqueous resin dispersion (D6).
(D6) Centrifugating 100 parts, adding 60 parts of water, centrifuging and solid-liquid separation was repeated twice, and then dried at 35 ° C. for 1 hour to obtain resin particles (P6). Table 1 shows the characteristic values of (P6).

<Comparative Example 1>
In the above <Example 1>, [Resin solution 1 ′] was obtained by the same method without adding triethylamine. The acid value of [resin solution 1 ′] is 11.2, the total amine value is 1.0, the tertiary amine value is 0, the absolute value of the difference between the acid value and the total amine value is 10.2, [acid value / Total amine number] was 11.7. Further, when 600 parts of [Aqueous phase 1] was added and dispersed in the same manner, once emulsified, water separated immediately and no resin particles were obtained.

<Comparative example 2>
In the above <Example 4>, [Resin solution 7] was obtained by the same method without adding triethylamine. [Resin solution 7] had an acid value of 12.5, a total amine value of 0, a tertiary amine value of 0, and an absolute value of the difference between the acid value and the total amine value of 12.5. Further, when 600 parts of [Aqueous phase 1] was added and dispersed in the same manner, emulsification was not performed, and water and the resin solution were separated, and resin particles were not obtained.

<Comparative Example 3>
In the above <Example 5>, [Resin solution 3 ′] was obtained by the same method without adding acetic acid and triethylamine. The acid value and total amine value of [resin solution 3 ′] were both 0. Furthermore, when 600 parts of [Aqueous phase 1] was added and dispersed in the same manner, water and the resin solution were separated without emulsification, and no resin particles were obtained.

<Comparative example 4>
[Polyester resin 1] 122 parts, ethyl acetate 188 parts, [urethane prepolymer solution 1] 27.2 parts, [curing agent 1] 0.6 parts, acetic acid 20.4 parts and triethylamine 40.8 parts in a beaker. The resulting mixture was dissolved and mixed and homogenized to obtain [Resin Solution 4 ′]. The acid value of [resin solution 4 ′] is 55.3, the total amine value is 57.2, the tertiary amine value is 56.6, and the absolute value of the difference between the acid value and the total amine value is 1.9. Value / total amine value] was 2.3. Further, in the same manner as in Example 1, when 600 parts of [Aqueous Phase 1] was added and dispersed, water was separated immediately after emulsification but resin particles were not obtained.

Physical property measurement example 1
The resin particles (P1) to (P6) obtained in Examples 1 to 6 were dispersed in water, and the particle size distribution was measured with Multitizer III. The residual amount of the tertiary amine was determined by using a gas chromatograph, creating a calibration curve for each target tertiary amine, and quantifying it based on the calibration curve.
All measurements were performed according to the method described above. The physical property measurement results are shown in Table 1. In all of the comparative examples, satisfactory resin particles were not obtained, so measurement could not be performed.

  Since the high-performance resin particles can be stably produced, the resin dispersion and resin particles obtained by the production method of the present invention are used as spacers for producing electronic parts such as slush molding resins, powder paints, liquid crystals, and electronic measuring instruments. It is extremely useful as resin particles useful for standard particles, toners used for electrophotography, electrostatic recording, electrostatic printing, various hot melt adhesives, and other molding materials.

Claims (15)

In the aqueous dispersion (W) of the resin particles (A) made of the resin (a), the resin (b), the precursor (b0) of (b), and one or more kinds selected from organic solvent solutions thereof are used. When the oily liquid (O) is dispersed and (b0) or a solution thereof is used, (b0) is further reacted, and in the aqueous dispersion of (A), the resin particles (B) comprising (b) are dispersed. A production method for obtaining an aqueous dispersion (X1) of resin particles (C) in which (A) is adhered to the surface of (B) by forming, wherein (O) has a weight average molecular weight of 1000 or less It contains a tertiary amine (c) and has an acid value of 1 to 50 mg KOH / g, a total amine value of 1 to 50 mg KOH / g, and a tertiary amine value of 0.1 to 50 mg KOH / g. A method for producing an aqueous resin dispersion. The production method according to claim 1, wherein the absolute value of the difference between the acid value of (O) and the total amine value is 10 or less, and [acid value / total amine value] is 0.2 to 5. (C) is one or more tertiary amines selected from aliphatic amines having 3 to 25 carbon atoms, heterocyclic amines having 3 to 25 carbon atoms, and aromatic amines having 6 to 25 carbon atoms. Item 3. The method according to Item 1 or 2. The manufacturing method according to any one of claims 1 to 3, wherein (C) comprises 0.1 to 50% by weight of (A) and 50 to 99.9% by weight of (B). The manufacturing method according to claim 1, wherein (C) has a structure in which 5% or more of the surface of (B) is covered with (A). (C) [Volume average particle diameter / number average particle diameter] is 1.0 to 1.5. The production method according to any one of claims 1 to 5. The volume average particle diameter of (A) is 0.0005 to 30 μm, the volume average particle diameter of (B) is 0.1 to 300 μm, and [volume average particle diameter of (A) / volume of (B). The average particle diameter] is 0.001 to 0.3, The manufacturing method in any one of Claims 1-6. The production method according to claim 1, wherein (a) and / or (b) is one or more resins selected from the group consisting of polyurethane resins, epoxy resins, vinyl resins and polyester resins. The production method according to claim 1, wherein (b0) comprises a prepolymer (α) having a reactive group and a curing agent (β). 10. (α) has at least one reactive group selected from the group consisting of an isocyanate group, a blocked isocyanate group and an epoxy group, and (β) is an active hydrogen group-containing compound (β1). Manufacturing method. In the aqueous resin dispersion (X1) obtained by the production method according to claim 1, after adhering (A) and (B) adhering to each other, (A ) Or a method of dissolving (A), and a method of producing an aqueous resin dispersion to obtain the aqueous resin dispersion (X2) of (B). The production method according to claim 11, wherein [B average particle size / number average particle size] of (B) is 1.0 to 1.5. The manufacturing method of the resin particle which removes an aqueous solvent from the aqueous resin dispersion obtained by the manufacturing method in any one of Claims 1-12. Resin particles obtained by the production method according to claim 13. 15. Resin particles according to claim 14, for use in slush molding resins, powder coatings, electronic component manufacturing spacers, standard particles for electronic measuring instruments, electrophotographic toners, electrostatic recording toners, electrostatic printing toners or hot melt adhesives .