JP2011026540A - Resin particle and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin particle which is excellent in preservability under a high-temperature and high-humidity condition and meltability at low temperature and which has a sufficiently narrow particle size distribution, and to provide a method for producing the resin particle by using a nonaqueous medium such as a supercritical fluid. <P>SOLUTION: The resin particle (C) is obtained by sticking a fine particle (A), which contains a crystalline resin (a) having (d1): alkyl (meth)acrylate having an 8-50C alkyl group, (d2): perfluoroalkyl alkyl (meth)acrylate and/or (d3): unsaturated dicarboxylic acid and/or anhydride thereof as essential constituent units, to the surface of another resin particle (B) containing a resin (b) or forming a film containing the crystalline resin (a) on the surface of the resin particle (B). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to resin particles and a method for producing the resin particles using a non-aqueous medium such as a liquid or supercritical fluid.

  Conventionally, as a particle formation method in a non-aqueous medium, a method of spraying a resin solution into a supercritical fluid (see, for example, Patent Documents 1 and 2), supercritical in the presence of a fine particle dispersant such as an organic pigment or silicon oxide. A method in which a resin melted by heating and melting in a fluid is mechanically dispersed to form fine particles and then reduced in pressure to obtain resin particles (see, for example, Patent Document 3), a supercritical fluid in the presence of a fine particle dispersant and an activator There is known a method (for example, Patent Documents 4 and 5) in which a resin solution is mechanically dispersed therein to form fine particles and then decompressed to obtain resin particles.

WO97 / 31691 pamphlet WO95 / 01221 pamphlet JP-A-2005-107405 JP 2006-321830 A JP 2007-277511 A

  According to the method of spraying the resin solution into the supercritical fluid, particles having excellent powder characteristics, electrical characteristics, etc., since no hydrophilic component is required and no surface active substance remains in the resin particles or on the surface. However, it is difficult to obtain a sharp particle size distribution. According to the above-mentioned method of dispersing a resin melted by heating in a supercritical fluid, it is said that particles having excellent powder characteristics, electrical characteristics, etc. and having a narrow particle size distribution can be obtained. It is difficult to say that the particle size distribution of the particles is sufficiently narrow. Further, in the technique of the above document, since the resin particle surface is coated with an organic pigment, silicon oxide or the like, there is a problem that the low-temperature meltability is inferior. According to the method of dispersing the resin solution in the supercritical fluid in the presence of the fine particle dispersant and the activator, it is difficult to obtain particles with a narrow particle size distribution because the resin particles are aggregated.

  An object of the present invention is to provide a production method for obtaining resin particles having a sufficiently narrow particle size distribution using a non-aqueous medium such as a resin particle having excellent low-temperature meltability and a sufficiently narrow particle size distribution and a liquid or supercritical fluid. To find.

The present invention has been made in view of the above circumstances in the prior art. That is, the present invention is the following five inventions.
(I) Resin particles (B) in which the fine particles (A) containing the crystalline resin (a) having the following (d1) and (d2) and / or (d3) as essential structural units contain the resin (b) Resin particles (C), wherein the resin particles (C) are fixed to the surface of the resin particles, or a film containing the crystalline resin (a) is formed on the surfaces of the resin particles (B).
(D1) alkyl (meth) acrylate having 8 to 50 carbon atoms in the alkyl group (d2) perfluoroalkyl (alkyl) (meth) acrylate (d3) unsaturated dicarboxylic acid and / or anhydride thereof (II) fine particles ( The liquid or supercritical carbon dioxide (X) in which A) is dispersed is mixed with a solution (L) in which the resin (b) is dissolved in the solvent (S), and (L) is mixed in (X). By dispersing, the resin particles (C1) in which the fine particles (A) are fixed to the surface of the resin particles (B1) containing the resin (b) and the solvent (S) are formed, and then liquid or supercritical carbon dioxide. The method for producing resin particles according to (I), comprising the step of obtaining resin particles (C) by removing (X) and the solvent (S).
(III) Liquid or supercritical carbon dioxide (X) in which the fine particles (A) are dispersed is mixed with the precursor (b0) of the resin (b), and (b0) is dispersed in (X). Further, the precursor (b0) is further reacted to form resin particles (C) in which the fine particles (A) are fixed on the surface of the resin particles (B) containing the resin (b), and then in a liquid or supercritical state. The method for producing resin particles according to (I), comprising the step of obtaining resin particles (C) by removing carbon dioxide (X).
(IV) Mixing liquid or supercritical carbon dioxide (X) in which the fine particles (A) are dispersed and a solution (L0) in which the precursor (b0) of the resin (b) is dissolved in the solvent (S). Then, (L0) is dispersed in (X), and the precursor (b0) is further reacted to form fine particles (A) on the surface of the resin particles (B1) containing the resin (b) and the solvent (S). Forming a resin particle (C1) to which is fixed, and then removing the liquid or supercritical carbon dioxide (X) and the solvent (S) to obtain the resin particle (C) ( A process for producing resin particles of I).
(V) The dispersion liquid in which the fine particles (A) are dispersed in the non-aqueous organic solvent (N) and the resin (b) or the precursor (b0) of the resin (b) are dissolved in the organic solvent (S1). When the organic solvent (S1) solution of the precursor (b0) is used, the precursor (b0) is further reacted, and the resin (b) ) -Containing resin particles (B) to form a non-aqueous dispersion of resin particles (C2) in which the fine particles (A) are fixed to the surfaces of the resin particles (B), and the non-aqueous dispersion The method for producing resin particles according to (I), comprising the step of obtaining resin particles (C) by removing the organic solvent (S1) and the non-aqueous organic solvent (N) from the liquid.

  The resin particles of the present invention and the resin particles obtained by the production method of the present invention have a sufficiently narrow particle size distribution, and the resin particles have good resistance to moisture and heat resistance and low temperature melting.

It is a flowchart of the experimental apparatus used for preparation of the resin particle in this invention.

The present invention is described in detail below.
The crystalline resin (a) used in the present invention has the following structural units (d1) and (d2) and / or (d3) [(d1) and (d2), (d1) and (d3), or A crystalline resin containing (d1), (d2) and (d3)], and further fixed to the surface of the resin particle (B) containing the resin (b), or the resin particle (B) Any type of resin can be used as long as it can form a film on its surface, and it may be a thermoplastic resin or a thermosetting resin.
(D1) alkyl (meth) acrylate having 8 to 50 carbon atoms in the alkyl group (d2) perfluoroalkyl (alkyl) (meth) acrylate (d3) unsaturated dicarboxylic acid and / or anhydride thereof (d1), and By containing (d2) and / or (d3), the storage stability under high temperature and high humidity is improved. Further, by containing (d2) and / or (d3), the chargeability under high temperature and high humidity is also improved.

The alkyl (meth) acrylate (d1) having 8 to 50 carbon atoms in the alkyl group has a linear or branched alkyl group. Specific examples thereof include 2-ethylhexyl (meth) acrylate and dodecyl (meta). ) Acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, and 2-decyltetradecyl (meth) acrylate. (D1) may be a single monomer or a combination of plural monomers. Among these, linear alkyl (meth) acrylates having 18 to 30 carbon atoms in the alkyl group are preferable, and behenyl (meth) acrylate is more preferable.
The content of (d1) in the crystalline resin (a) is preferably 30 to 90%, more preferably 40 to 85%, and particularly preferably 50 to 80%. When the content of (d1) is 30% or more, it has crystallinity and is sharp-melted, so that it has excellent storage stability and low-temperature meltability, and good charging characteristics under high temperature and high humidity, and is 90% or less. Charging characteristics under high temperature and high humidity are better.
In the above and below, “%” means “% by weight” unless otherwise specified.

The perfluoroalkyl (alkyl) (meth) acrylate (d2) is preferably a perfluoroalkyl group having an even number of 2 to 12 carbon atoms and a (alkyl) moiety having 0 to 3 carbon atoms. Specific examples include (2-perfluoroethyl) ethyl (meth) acrylate, (2-perfluorobutyl) ethyl (meth) acrylate, (2-perfluorohexyl) ethyl (meth) acrylate, (2-perfluorooctyl). ) Ethyl (meth) acrylate, (2-perfluorodecyl) ethyl (meth) acrylate, and (2-perfluorododecyl) ethyl (meth) acrylate. 2,2,2-trifluoroethyl acrylate is also preferred. (D2) may be a single monomer or a combination of plural monomers.
Of these, more preferred are (2-perfluorohexyl) ethyl (meth) acrylate, (2-perfluorooctyl) ethyl (meth) acrylate, and (2-perfluorodecyl) ethyl (meta) from the viewpoint of chargeability. ) Acrylate, (2-perfluorododecyl) ethyl (meth) acrylate.
In addition, the said (meth) acrylate means an acrylate and / or a methacrylate, and the same description method is used hereafter.

The unsaturated dicarboxylic acid and / or its anhydride (d3) is preferably an unsaturated dicarboxylic acid having 3 to 30 carbon atoms and its anhydride. Specific examples thereof include maleic acid, fumaric acid, maleic anhydride, and itaconic acid. , Itaconic anhydride, citraconic acid, citraconic anhydride and the like. (D3) may use 2 or more types together. Of these, maleic anhydride is more preferable from the viewpoint of chargeability.
The content (total) of (d2) and / or (d3) in the crystalline resin (a) is preferably 0.001 to 30%, more preferably 0.005 to 25%, more preferably 0.01. -20%, particularly preferably 0.1-10%, most preferably 0.1-5%. When the content of (d2) and / or (d3) is 0.001% or more, the charging characteristics under high temperature and high humidity are good, and when it is 30% or less, the crystallinity increases and the storage stability is increased. Property is improved.
The total content of monomers other than (d1), (d2), and (d3) in (a) is preferably 50% or less, more preferably 30% or less. When the content of the monomer other than (d1), (d2), and (d3) is 50% or less, the degree of crystallinity is increased and the storage stability is improved.

Examples of the crystalline resin (a) include vinyl resins, polyurethane resins, polyurea resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomers. Examples thereof include resins and polycarbonate resins. As the resin (a), two or more of the above resins may be used in combination. Among these, a vinyl resin, a polyurethane resin, and a polyurea resin are preferable from the viewpoint that a liquid or supercritical carbon dioxide (X) dispersion or a non-aqueous organic solvent (N) dispersion of resin particles is easily obtained. Epoxy resins, polyester resins, and combinations thereof, more preferably vinyl resins, aliphatic or aromatic polyester resins, and aliphatic polyurethanes and / or polyurea resins, particularly preferably one of the monomers to be added copolymerized. As alkyl (meth) acrylate (d1), perfluoroalkyl (alkyl) (meth) acrylate (d2) having an alkyl group having 8 to 50 carbon atoms, and unsaturated dicarboxylic acid and / or anhydride thereof (d3) ) Is a vinyl resin from the viewpoint of easy introduction of structural units.
In the case of other than a vinyl resin, after synthesizing a vinyl polymer having the structural units (d1) and (d2) and / or (d3), a reaction such as esterification or amidation is performed, or a vinyl group (D1) and (d2) and / or (d3) are copolymerized with a resin other than these vinyl resins having

Hereinafter, the vinyl resin which is a preferable resin as (a) will be described in detail.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer, and an alkyl (meth) acrylate (d1) or a perfluoroalkyl (alkyl) (meth) acrylate (d2) having an alkyl group having 8 to 50 carbon atoms. Examples of vinyl monomers other than unsaturated dicarboxylic acid and / or anhydride (d3) thereof include the following (1) to (10).

(1) Vinyl hydrocarbons:
(1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, α-olefins other than the above, etc .; alkadienes such as butadiene , Isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene, limonene, Inden etc.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutes, such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethyl Styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, and the like; and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomers other than (d3) and metal salts thereof:
C3-C30 unsaturated monocarboxylic acid, monoalkyl (C1-C24) ester of unsaturated dicarboxylic acid, for example, (meth) acrylic acid, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, crotonic acid, Carboxyl group-containing vinyl monomers such as itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid monoalkyl ester, cinnamic acid and the like. In addition, the said (meth) acrylic acid means acrylic acid and / or methacrylic acid, and uses the same description method hereafter. The alkyl chain constituting the monoalkyl (C1-24) ester preferably has a branched structure from the viewpoint of improving hydrolysis resistance.

(3) Sulfone group-containing vinyl monomers, vinyl sulfate monoesters and their salts: Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid And alkyl derivatives thereof having 2 to 24 carbon atoms, such as α-methylstyrene sulfonic acid, etc .; sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy- 3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxy Propanesulfonic acid, 2- (me ) Acrylamide-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid, poly (n = 2 to 30) oxyalkylene (ethylene, propylene) , Butylene: single, random or block) mono (meth) acrylate sulfate [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and the following general Sulfate ester or sulfonic acid group-containing monomers represented by formulas (1-1) to (1-3); and salts thereof.

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

CH = CH-CH ₃
｜
R-Ar-O- (AO) nSO 3 H (1-2)

CH ₂ COOR '
｜
HO ₃ SCHCOOCH ₂ CH (OH) CH ₂ OCH ₂ CH═CH ₂ (1-3)

(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, and when they are different, they may be random or block. Ar represents a benzene ring, n represents an integer of 1 to 50, and R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom.

(4) Phosphoric acid group-containing vinyl monomer and salt thereof:
(Meth) acryloyloxyalkyl (C1 to C24) phosphoric acid monoester, for example, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) Phosphonic acids, such as 2-acryloyloxyethylphosphonic acid.

  Examples of the salts (2) to (4) include metal salts, ammonium salts, and amine salts (including quaternary ammonium salts). Examples of the metal forming the metal salt include Al, Ti, Cr, Mn, Fe, Zn, Ba, Zr, Ca, Mg, Na, and K. Alkali metal salts and amine salts are preferred, and sodium salts, magnesium salts, aluminum salts, tertiary monoamines having 3 to 20 carbon atoms, and diamine salts are more preferred.

(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, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, salts thereof, etc. (6-2) Amido group Vinyl monomers: (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 monomers: (meth) acrylonitrile, cyanostyrene (6-4) quaternary ammonium cation group-containing vinyl monomers: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethyl Aminoethyl (meth) acrylamide, quaternized product of tertiary amine group-containing vinyl monomers such as diallylamine (methyl chloride, dimethyl sulfate, benzyl chloride, which was quaternized with quaternizing agents such as dimethyl carbonate)
(6-5) Nitro group-containing vinyl monomer: nitrostyrene, etc.

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

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

(9) Vinyl esters other than (d1) and (d2), vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl butyrate, vinyl acetate, 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 1 to 7 carbon atoms of alkyl group [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, etc.], dialkyl fumarate (dialkyl fumarate ester) (two alkyl groups are linear, branched or alicyclic having 2 to 8 carbon atoms. Dialkyl maleates (dialkyl maleates) (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxy Alkanes [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol [several Average molecular weight (hereinafter abbreviated as Mn) 300] mono (meth) acrylate, polypropylene glycol (Mn500) monoacrylate, methyl alcohol ethylene oxide (ethylene oxide is abbreviated as EO hereinafter) 10 mol adduct (meth) acrylate, lauryl alcohol With EO 30 mol Additives (meth) acrylates, etc.], poly (meth) acrylates [poly (meth) acrylates of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.].
(9-2) Vinyl (thio) ether, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxy butadiene, vinyl 2- Butoxyethyl ether, 3,4-dihydro1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, etc. (9-3) Vinyl ketones such as vinyl Methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone;
Vinyl sulfones, such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, etc.

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

  As a copolymer of vinyl monomers, (d1), and (d2) and / or (d3) are essential monomers, and if necessary, any monomers selected from the monomers (1) to (10) described above, Examples thereof include polymers copolymerized at an arbitrary ratio in the number of two or more. For example, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate copolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate-methyl (meth) acrylate copolymer Compound, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate- (meth) acrylic acid-methyl (meth) acrylate copolymer, (2-perfluorododecyl) ethyl (meth) acrylate- Behenyl (meth) acrylate-acrylonitrile copolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate-maleic anhydride copolymer, (2-perfluorododecyl) ethyl (meth) acrylate Behenyl (meth) acrylate (Meth) acrylic acid copolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate-styrene copolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) Acrylate-hydroxyethyl (meth) acrylate copolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate-acrylonitrile-maleic anhydride-methyl (meth) acrylate-hydroxyethyl (meth) acrylate Copolymer, behenyl (meth) acrylate-maleic anhydride copolymer, behenyl (meth) acrylate-methyl (meth) acrylate-maleic anhydride copolymer, (2-perfluorodecyl) ethyl (meth) acrylate Behenyl (meta) aqua Rate - styrene - fumaric acid copolymer, and the like.

  Examples of the method for producing the crystalline vinyl resin include known vinyl monomer polymerization methods such as solution polymerization, bulk polymerization and suspension polymerization.

  As for the crystalline resin (a), a resin other than the vinyl resin, for example, an aliphatic or aromatic polyester resin, an aliphatic polyurethane and / or a polyurea resin will be described.

  Examples of the polyester resin, polyurethane resin, and polyurea resin include alkyl (meth) acrylate (d1), perfluoroalkyl (alkyl) (meth) acrylate (d2), unsaturated dicarboxylic acid having an alkyl group having 8 to 50 carbon atoms, and / Or at least one of its anhydride (d3) and a vinyl resin having a hydroxyl group-containing vinyl monomer as a constituent unit and a composite resin obtained by urethanization of the above resin with diisocyanate, the vinyl resin and the above-mentioned carboxyl group-containing compound A composite resin such as a composite resin obtained by reacting with a resin can be used.

As the aliphatic or aromatic polyester resin, diol (11) and dicarboxylic acid (13) described later can be used, and in particular, a linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms and 2 to 2 carbon atoms. A linear aliphatic dicarboxylic acid having 50 alkylene chains is an essential constituent unit, and the total number of carbon atoms of the alkylene chain of the diol and the alkylene chain of the dicarboxylic acid is 10 to 52, as necessary A crystalline polyester resin (a1) having an aromatic dicarboxylic acid having 6 to 30 carbon atoms as a structural unit is preferred.
In the aliphatic or aromatic polyester resin, from the viewpoint of storage stability, the total number of carbon atoms of the alkylene chain of the diol and the alkylene chain of the dicarboxylic acid is preferably 10 or more, more preferably 12 or more. Yes, particularly preferably 14 or more. Further, from the viewpoint of fixability, it is preferably 52 or less, more preferably 45 or less, and particularly preferably 40 or less.

From the viewpoint of crystallinity, the number of carbon atoms in the linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more. . From the viewpoint of fixability, it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic diol are 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol.
From the standpoint of crystallinity, the number of carbon atoms in the linear aliphatic dicarboxylic acid alkylene chain having 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more. . From the viewpoint of fixability, it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic dicarboxylic acid are adipic acid, sebacic acid, dodecanedicarboxylic acid, and octadecanedicarboxylic acid.
Moreover, from the viewpoint of storage stability of the aromatic polyester resin, the aromatic dicarboxylic acid preferably has 8 to 30 carbon atoms, more preferably 8 to 24 carbon atoms, and particularly preferably 8 to 20 carbon atoms. Preferable examples of the aromatic dicarboxylic acid having 6 to 30 carbon atoms are phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid.

  In the case of an aromatic polyester resin, from the viewpoint of resin strength, the dicarboxylic acid is preferably a combination of a linear aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and the aromatics based on the total of the linear aliphatic dicarboxylic acid and the aromatic dicarboxylic acid. The ratio of the group dicarboxylic acid is preferably 90% or less, more preferably 1 to 85%, and particularly preferably 3 to 80%.

Examples of the aliphatic polyurethane resin, the aliphatic polyurea resin, and the aliphatic polyurethane / polyurea resin include a diol (11) described below, a diamine (a divalent one of the polyamine (16) described below), and a diisocyanate (a polyisocyanate described below). (15) is a divalent one, and in particular, a linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms and / or a linear aliphatic having an alkylene chain having 2 to 50 carbon atoms. A diamine and a linear aliphatic diisocyanate having an alkylene chain having 2 to 50 carbon atoms are essential structural units, and the total carbon number of the alkylene chain of the diol and / or diamine and the alkylene chain of the diisocyanate A crystalline polyurethane and / or polyurea resin (a2) having a number of 10 to 52 is preferred.
A linear aliphatic diisocyanate having a polyester diol obtained by reacting a linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms with a dicarboxylic acid (13) described later and an alkylene chain having 2 to 50 carbon atoms. (A2) is also included in the polyurethane resin obtained from
From the viewpoint of storage stability, the aliphatic polyurethane and / or polyurea resin has a carbon number of alkylene chains of diol and / or diamine (if a mixture of diol and diamine is used, the number of alkylene chains averaged by the weight ratio thereof). The total number of carbon atoms in the alkylene chain of the diisocyanate is preferably 10 or more, more preferably 12 or more, and particularly preferably 14 or more. Further, from the viewpoint of fixability, it is preferably 52 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less.

The preferred carbon number of the alkylene chain and preferred specific examples of the linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms are the same as in the crystalline polyester resin (a1).
From the viewpoint of crystallinity, the number of carbon atoms in the alkylene chain of the linear aliphatic diamine having an alkylene chain having 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more. . From the viewpoint of fixability, it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic diamine are tetramethylene diamine and hexamethylene diamine.
In addition, the number of carbon atoms in the alkylene chain of the linear aliphatic diisocyanate having an alkylene chain having 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more from the viewpoint of crystallinity. It is. From the viewpoint of fixability, it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic diisocyanate are tetramethylene diisocyanate and hexamethylene diisocyanate.

  The aliphatic or aromatic polyester resin can be produced by reacting a low molecular polyol and / or a polyalkylene ether diol having an Mn of 1000 or less with a polycarboxylic acid, a method by ring-opening polymerization of a lactone, a low molecular diol and a lower alcohol. Known production methods such as a method of reacting with a carbonic acid diester (such as methanol) can be mentioned.

  Examples of the production method of the aliphatic polyurethane and / or polyurea resin include known production methods such as a method of reacting a low molecular weight polyol (including the polyester polyol obtained by the above method) and / or a low molecular weight diamine with a diisocyanate. .

  The melting point of the crystalline resin (a) is preferably 40 to 110 ° C, more preferably 45 to 100 ° C, particularly preferably 50 to 90 ° C. If the melting point of the crystalline resin (a) is 40 ° C. or higher, the resin particles (C) of the present invention are difficult to block even during long-term storage. If it is 110 degrees C or less, low-temperature meltability is favorable. The melting point can be measured from an endothermic peak in differential scanning calorimetry (hereinafter referred to as DSC).

The degree of crystallinity of the crystalline resin (a) is preferably 20 to 95% from the viewpoint of suppressing swelling due to carbon dioxide (X) in a liquid or supercritical state and adsorbability to the resin particles (B). More preferably, it is 30 to 80%. The degree of crystallinity is obtained by calculating the heat of fusion (ΔHm (J / g)) from the area of the endothermic peak using DSC, and calculating the degree of crystallinity (%) by the following formula based on the measured ΔHm.
Crystallinity = (ΔHm / a) × 100
In the above formula, a is the heat of fusion when extrapolated so that the degree of crystallinity is 100%.

  Mn of the crystalline resin (a) is preferably 1000 or more, more preferably 1500 or more, particularly preferably 2000 or more, from the viewpoint of resin strength. Moreover, from a viewpoint of melt viscosity, Preferably it is 1 million or less, More preferably, it is 500,000 or less, Most preferably, it is 300000 or less.

The fine particles (A) containing the crystalline resin (a) may contain an amorphous resin (a ′) in addition to (a). The melting point of the mixture of (a) and (a ′) is preferably 40 to 150 ° C. The content of (a ′) is preferably 0 to 50% with respect to the total weight of (a) and (a ′). Moreover, the microparticles | fine-particles which coat | covered amorphous resin (a ') with crystalline resin (a) may be sufficient.
As an amorphous resin (a '), what is not crystalline in resin (b) mentioned later is mentioned.

  The production method of the fine particles (A) may be any production method, but as a specific example, a dry production method [the crystalline resin (a) constituting the fine particles (A) is a known dry pulverizer such as a jet mill, etc. Method of dry pulverization by the above], method of manufacturing by wet [dispersion of the powder of (a) in an organic solvent and wet pulverization by a known wet disperser such as a bead mill or a roll mill, spraying the solvent solution of (a) A method of spray-drying with a drier, etc., a method of supersaturating the solvent solution of (a) by adding a poor solvent or cooling, a method of dispersing the solvent solution of (a) in water or an organic solvent, a precursor of (a) Can be polymerized by emulsion polymerization, soap-free emulsion polymerization, seed polymerization, suspension polymerization, or the like in water, or the method of polymerizing the precursor (a) by dispersion polymerization in an organic solvent].In addition, after the fine particles (A ′) of the amorphous resin (a ′) are synthesized by the above method, the crystalline resin (a) is converted to the surface of (A ′) by a known coating method, seed polymerization method, mechanochemical method, or the like. You may form in. Among these, from the viewpoint of easy production of the fine particles (A), a wet production method is preferable, and a precipitation method, an emulsion polymerization method, and a dispersion polymerization are more preferable.

  The fine particles (A) may be used as they are, and for example, silane is used in order to impart the adsorptivity to the resin particles (B) or to modify the powder characteristics and electrical characteristics of the resin particles (C) of the present invention. The surface may be modified by surface treatment with a coupling agent such as a system, titanate or aluminate, surface treatment with various surfactants, coating treatment with a polymer, or the like. It is preferable that either one of the fine particles (A) and the resin particles (B) has an acidic functional group on at least its surface, and the other has at least a basic functional group on its surface.

  The fine particles (A) and the resin particles (B) may have an acidic functional group or a basic functional group therein. Examples of the acidic functional group include a carboxylic acid group and a sulfonic acid group. Examples of basic functional groups include primary amino groups, secondary amino groups, and tertiary amino groups.

  The fine particles (A) and the resin particles (B) have an acidic functional group or a basic functional group as the crystalline resin (a) and the resin (b) in order to impart at least an acidic functional group or a basic functional group to the surface thereof. You may use the resin which has, and in order to provide these functional groups to microparticles | fine-particles (A) and resin particle (B), you may surface-treat.

  Examples of the crystalline resin (a) having an acidic functional group include an aliphatic polyester resin having an acid value and a monomer having an acidic functional group (for example, the aforementioned carboxyl group-containing vinyl monomer, sulfone group-containing vinyl monomer). Examples thereof include a copolymerized vinyl resin.

  Examples of the crystalline resin (a) having a basic functional group include a vinyl resin obtained by copolymerizing a monomer having a basic functional group (for example, the aforementioned amino group-containing vinyl monomer).

  The resin particles (B) are composed of the resin (b). In the present invention, as the resin (b), a thermoplastic resin (b1), a resin (b2) obtained by finely crosslinking the thermoplastic resin, or a polymer blend containing a thermoplastic resin as a sea component and a cured resin as an island component ( b3), and two or more of them may be used in combination. Examples of the thermoplastic resin (b1) include vinyl resins, polyurethane resins, epoxy resins, and polyester resins. Among these, a vinyl resin, a polyurethane resin, a polyester resin, and a combination thereof are preferable from the viewpoint that a dispersion of fine spherical resin particles is easily obtained.

  The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. As the vinyl monomer, the same ones as described above can be used, but alkyl (meth) acrylate (d1) and perfluoroalkyl (alkyl) (meth) acrylate (d2) in which the alkyl group has 8 to 50 carbon atoms. , And unsaturated dicarboxylic acid and / or its anhydride (d3) may not be used.

Examples of polyester resins include polycondensates of polyols and polycarboxylic acids (including acid anhydrides and lower alkyl esters thereof). Examples of the polyol include a diol (11) and a trivalent or higher polyol (12), and examples of the polycarboxylic acid include a dicarboxylic acid (13) and a trivalent or higher polycarboxylic acid (14).
The reaction ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/1, more preferably 1.5 / 1, as the 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.

  Diol (11) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, Tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol) An alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; an alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above bisphenol; Examples include polylactone diol (such as poly ε-caprolactone diol) and polybutadiene diol. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.

  Examples of the trihydric or higher polyol (12) include 3 to 8 or higher polyhydric aliphatic alcohols (such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol); trisphenols (such as trisphenol PA) ); Novolak resins (phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trisphenols; alkylene oxide adducts of the above novolac resins, acrylic polyols [copolymers of hydroxyethyl (meth) acrylate and other vinyl monomers Etc.].

  Dicarboxylic acids (13) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, dodecenyl succinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.) Branched alkylene dicarboxylic acid having 8 or more carbon atoms [dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.), alkyl succinic acid (decyl succinic acid, dodecyl succinic acid, octadecyl) Succinic acid); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.

  Examples of the trivalent or higher (3 to 6 or higher) polycarboxylic acid (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).

  As the dicarboxylic acid (13) or the trivalent or higher polycarboxylic acid (14), acid anhydrides or lower alkyl esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

  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 (excluding carbon in NCO group, the same shall apply hereinafter) 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), 2,4′- and / or Or 4,4'-diphenylmethane diisocyanate (MDI) etc. are mentioned.
Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and the like.
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, and methylcyclohexylene diisocyanate (hydrogenated TDI). .
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.

The following are mentioned as an example of a polyamine (16).
Aliphatic polyamines (C2 to C18):
[1] Aliphatic polyamine {C2-C6 alkylenediamine (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) polyamine [diethylenetriamine, etc.}}
[2] These alkyl (C1-C4) or hydroxyalkyl (C2-C4) substituted products [dialkyl (C1-C3) aminopropylamine, etc.]
[3] Alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc.]
[4] Aromatic ring-containing aliphatic amines (C8 to C15) (such as xylylenediamine, tetrachloro-p-xylylenediamine),
-Alicyclic polyamines (C4 to C15): 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.
Aromatic polyamines (C6-C20):
[1] Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine and the like; nucleus-substituted alkyl group [C1-C4 alkyl such as methyl, ethyl, n- and i-propyl, butyl, etc.] Aromatic polyamines such as 2,4- and 2,6-tolylenediamine etc.), and mixtures of various proportions of these isomers [2] nuclear substituted electron withdrawing groups (Cl, Br, I, Aromatic polyamines having halogens such as F; alkoxy groups such as methoxy and ethoxy; nitro groups and the like
[3] Aromatic polyamine having a secondary amino group [Any or all of —NH ₂ of the aromatic polyamines (4) to (6) above is —NH—R ′ (R ′ is a lower group such as methyl, ethyl, etc.) Substituted with an alkyl group] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.],
Heterocyclic polyamines (C4 to C15): piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, etc.
Polyamide polyamines: low molecular weight polyamide polyamines obtained by condensation of dicarboxylic acids (such as dimer acids) and excess (more than 2 moles per mole of acid) polyamines (such as alkylene diamines, polyalkylene polyamines, etc.)
-Polyether polyamine: hydride of cyanoethylated polyether polyol (polyalkylene glycol, etc.).

  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) 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 (molecular weight per epoxy group) of the polyepoxide (18) is preferably 65 to 1000, and more preferably 90 to 500. When the epoxy equivalent is 1000 or less, the crosslinked structure becomes dense and the physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are improved. On the other hand, those having an epoxy equivalent of 65 or more are synthesized. Easy.

  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 the glycidyl ether of polyhydric phenol include bisphenol F diglycidyl ether and bisphenol A diglycidyl ether. 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, as the aromatic polyepoxy compound, triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, polyol in the two reactants Also included are glycidyl group-containing polyurethane (pre) polymers obtained by reaction and diglycidyl ethers of alkylene oxide (ethylene oxide or propylene oxide) adducts of bisphenol A. Examples of the heterocyclic polyepoxy compound include trisglycidylmelamine. Examples of the alicyclic polyepoxy compound include vinylcyclohexene dioxide. The alicyclic polyepoxy compound 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. Examples of polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether. Examples of 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 polyepoxy compound 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 polyepoxides may be used in combination.

  The resin (b2) obtained by microcrosslinking a thermoplastic resin refers to a resin in which a crosslinked structure is introduced and the Tg of the resin (b) is 20 to 200 ° C. Such a cross-linked structure may be any cross-linked form such as covalent bond, coordinate bond, ionic bond, hydrogen bond, and the like. As a specific example, for example, when a polyester is selected as the resin (b2), a crosslinked structure is introduced by using a polyol or polycarboxylic acid at the time of polymerization, or a compound having a functional group number of 3 or more in both. be able to. When a vinyl resin is selected as the resin (b2), a crosslinked structure can be introduced by adding a monomer having two or more double bonds during polymerization.

  The polymer blend (b3) having a thermoplastic resin as a sea component and a cured resin as an island component has a Tg of 20 to 200 ° C. and a softening start temperature of 40 to 220 ° C., specifically vinyl resin and polyester Resins, polyurethane resins, epoxy resins and mixtures thereof.

  The Mn of the resin (b) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000, and the solubility parameter (SP value, details will be described later) is preferably 7 to 18, more preferably. 8-14. Moreover, when it is desired to modify the thermal characteristics of the resin particles (C) of the present invention, the resin (b2) or the resin (b3) may be used.

  The glass transition temperature (Tg) of the resin (b) is preferably 20 ° C to 200 ° C, more preferably 40 ° C to 150 ° C. Above 20 ° C, the storage stability of the particles is good. In addition, Tg in this invention is a value calculated | required from DSC measurement.

  The softening start temperature of the resin (b) is preferably 40 ° C to 220 ° C, more preferably 50 ° C to 200 ° C. Above 40 ° C, long-term storage is good. Below 220 ° C., the fixing temperature does not increase and there is no problem. In addition, the softening start temperature in this invention is a value calculated | required from a flow tester measurement.

  The volume average particle size of the resin particles (B) is preferably 1 to 10 μm, more preferably 2 to 8 μm.

  The resin particles (C) of the present invention have a fine particle (A) fixed on the surface of the resin particle (B) or a film in which the fine particles (A) are formed on the surface of the resin particle (B). It is a particle formed. The fine particles (A) fixed on the surface of the resin particles (B) do not include the case where (A) simply adheres to the surface of (B) and easily desorbs.

  The particle size of the fine particles (A) is smaller than the particle size of the resin particles (B). The value of particle size ratio [volume average particle size of fine particles (A) / [volume average particle size of resin particles (C) of the present invention]] is preferably 0.001 to 0.3, more preferably 0.002 to 0.002. It is 0.2, more preferably 0.003 to 0.1, and particularly preferably 0.01 to 0.08. Within the above range, (A) is efficiently adsorbed on the surface of (B), so the particle size distribution of the obtained resin particles (C) of the present invention becomes narrow.

  The volume average particle diameter of the fine particles (A) is preferably 0.01 to 0.5 μm, and particularly preferably 0.015 to 0.4 μm. The volume average particle size is determined by a dynamic light scattering particle size distribution measuring device (for example, LB-550: manufactured by Horiba Seisakusho), a laser type particle size distribution measuring device (for example, LA-920: manufactured by Horiba Seisakusho), Multisizer III (Beckman).・ Measured by Coulter, Inc.

  The volume average particle diameter of the resin particles (C) of the present invention is preferably 1 to 10 μm, more preferably 2 to 8 μm, and further preferably 3 to 6 μm. When it is 1 μm or more, handling properties as a powder are improved. When it is 10 μm or less, the melting characteristics are improved.

  The ratio of the volume average particle diameter DV of the resin particles (C) of the present invention to the number average particle diameter DN of the resin particles (C) of the present invention: DV / DN is preferably 1.0 to 1.5, more preferably Is 1.0 to 1.4, particularly preferably 1.0 to 1.3. When it is 1.5 or less, powder characteristics (fluidity, charging uniformity, etc.) and melting characteristics are remarkably improved.

From the viewpoint of particle size uniformity, powder flowability, storage stability, etc., 5% or more of the surface of the resin particles (B) is composed of fine particles (A) or (A ) Is preferably covered with a film derived from the above, more preferably 30% or more. 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 (%) = [(A) or (B) surface area of the portion covered with the coating derived from (A) / {(A) or (the portion covered with the coating derived from (A) ( B) surface area + (B) exposed surface area}] × 100

In the resin particles (C) of the present invention, the weight ratio of the crystalline resin (a) constituting the fine particles (A) and the resin (b) constituting the resin particles (B) is preferably (0.1: 99. 9) to (30:70), and more preferably (0.2: 99.8) to (20:80). It is preferable that the weight ratio of the crystalline resin (a) and the resin (b) is within this range because both low-temperature meltability and long-term storage stability are compatible.
The weight ratio of the crystalline resin (a) in the resin particles (C) of the present invention can be measured by a known method, for example, a method of calculating from the endothermic peak of the endothermic peak unique to (a) by DSC.

The resin particles (C) of the present invention may be described as liquid or supercritical carbon dioxide (X) [hereinafter referred to as carbon dioxide (X). ], It is preferable to obtain by the following production method.
Manufacturing Method (1) [Second Invention]
By mixing carbon dioxide (X) in which the fine particles (A) are dispersed and a solution (L) in which the resin (b) is dissolved in the solvent (S), (L) is dispersed in (X). The resin particles (B1) containing the resin (b) and the solvent (S) are formed on the surfaces of the resin particles (C1), and then the carbon dioxide (X) and the solvent (S) are removed. The manufacturing method which obtains the resin particle by doing.
Manufacturing Method (2) [Third Invention]
Carbon dioxide (X) in which the fine particles (A) are dispersed and the precursor (b0) of the resin (b) are mixed, (b0) is dispersed in (X), and the precursor (b0) is further reacted. To form resin particles (C) in which fine particles (A) are fixed on the surface of resin particles (B) containing resin (b), and then removing carbon dioxide (X) to obtain resin particles. Production method.
Manufacturing Method (3) [Fourth Invention]
Carbon dioxide (X) in which the fine particles (A) are dispersed and a solution (L0) in which the precursor (b0) of the resin (b) is dissolved in the solvent (S) are mixed, and (L0) ) And further reacting the precursor (b0), the resin particles (C1) in which the fine particles (A) are fixed to the surfaces of the resin particles (B1) containing the resin (b) and the solvent (S) are obtained. A method for producing resin particles by forming and then removing carbon dioxide (X) and solvent (S).

Moreover, when manufacturing the resin particle of this invention in a non-aqueous organic solvent (N), it is preferable to obtain with the following manufacturing methods.
Manufacturing Method (4) [Fifth Invention]
A dispersion in which fine particles (A) are dispersed in a non-aqueous organic solvent (N), and a solution in which the resin (b) or the precursor (b0) of the resin (b) is dissolved in the organic solvent (S1) When the organic solvent (S1) solution of the precursor (b0) is used, the precursor (b0) is further reacted to contain the resin (b) in the fine particle (A) dispersion. By forming the resin particles (B) to be formed, a non-aqueous dispersion of the resin particles (C2) in which the fine particles (A) are fixed to the surfaces of the resin particles (B) is formed, and further, from the non-aqueous dispersion, A production method for obtaining resin particles by removing the organic solvent (S1) and the non-aqueous organic solvent (N).

The production method (1) will be described in detail.
The fine particles (A) described above can be used as the fine particles (A) used in the production method of the present invention. The same applies to the manufacturing methods (2), (3), and (4).

The insoluble content of the resin (b) with respect to the solvent (S) in the equal weight mixture of the resin (b) and the solvent (S) in the standard state (23 ° C., 0.1 MPa) is based on the weight of the resin (b). , Preferably 20% or less, more preferably 15% or less. If the insoluble matter weight is 20% or less, the particle size distribution of the obtained resin particles becomes narrow.
The same applies to the case where the precursor (b0) is used instead of the resin (b) in the production method (3), and the case where a mixture of the resin (b) and the precursor (b0) is used.

Moreover, 9-16 are preferable and, as for the solubility parameter (SP value) of a solvent (S), More preferably, it is 10-15. The SP value is expressed by the square root of the ratio between the cohesive energy density and the molecular volume, as shown below.
SP = (△ E / V) ^1/2
Here, ΔE represents the cohesive energy density. V represents the molecular volume, and its value is Robert F. Based on calculations by Robert F. Fedors et al., For example, described in Polymer Engineering and Science, Vol. 14, pages 147-154.

Examples of the solvent (S) include ketone solvents (acetone, methyl ethyl ketone, etc.), ether solvents (tetrahydrofuran, diethyl ether, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, cyclic ether, etc.), ester solvents (acetate ester, pyrubin). Acid esters, 2-hydroxyisobutyric acid esters, lactic acid esters, etc.), amide solvents (dimethylformamide, etc.), alcohol solvents (methanol, ethanol, isopropanol, fluorine-containing alcohols, etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.), And aliphatic hydrocarbon solvents (octane, decane, etc.). A mixed solvent of two or more of these solvents, or a mixed solvent of these organic solvents and water can also be used.
Preferably, from the viewpoint of easy particle formation, a mixed solvent (particularly, a mixed solvent of acetone, methanol and water, a mixed solvent of acetone and methanol, a mixed solvent of acetone and ethanol, and a mixed solvent of acetone and water) is used. is there.
The same applies to the solvent (S) and the organic solvent (S1) in the production methods (3) and (4).

The solution (L) of the resin (b) is produced by dissolving the resin (b) in the solvent (S). The concentration of the resin (b) is preferably 10 to 90%, more preferably 20 to 80% with respect to the weight of the solution (L).
The concentration of the precursor (b0) in the organic solvent (S1) solution of the solutions (L0) and (b0) in the production methods (3) and (4) is also the same.

  In the dispersion step of dispersing the resin (b) solution (L) in the production method (1) in carbon dioxide (X), the following dispersion stabilizer (E) can be used. The dispersion stabilizer (E) is a compound having at least one of a dimethylsiloxane group and a functional group containing fluorine. Furthermore, it is preferable to have a chemical structure having affinity for the resin (b) together with a dimethylsiloxane group and a fluorine-containing group having affinity for carbon dioxide.

For example, when the resin (b) is a vinyl resin, the dispersion stabilizer (E) is preferably a vinyl resin having a monomer having at least one of a dimethylsiloxane group and a functional group containing fluorine as a structural unit. .
As the monomer (or reactive oligomer) (M1-1) having a dimethylsiloxane group, methacryl-modified silicone is preferable and has a structure represented by the following formula.
(CH ₃ ) ₃ SiO ((CH ₃ ) ₂ SiO) aSi (CH ₃ ) ₂ R
However, a is an average value of 15-45, and R is an organic modification group containing a methacryl group. An example of R includes —C ₃ H ₆ OCOC (CH ₃ ) ═CH ₂ .

  Specific examples of the fluorine-containing monomer (M1-2) include perfluoroolefins such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and chlorotrifluoroethylene (CTFE); perfluoro (alkyl vinyl ether) ) (PFAVE), perfluoro (1,3-dioxole), perfluoro (2,2-dimethyl-1,3-dioxole) (PFDD), perfluoro- (2-methylene-4-methyl-1,3- Peroxo vinyl ethers such as dioxolane) (MMD), perfluorobutenyl vinyl ether (PFBVE); vinylidene fluoride (VdF), trifluoroethylene, 1,2-difluoroethylene, vinyl fluoride, trifluoropropylene, 3, 3, 3-trifluoro-2-to Hydrogen-containing fluoroolefins such as fluoromethylpropene, 3,3,3-trifluoropropene, perfluoro (butyl) ethylene (PFBE); 1,1-dihydroperfluorooctyl acrylate (DPFOA), 1,1-dihydroper Fluorooctyl methacrylate (DPFOMA), 2- (perfluorooctyl) ethyl acrylate (PFOEA), 2- (perfluorooctyl) ethyl methacrylate (PFOEMA), 2- (perfluorohexyl) ethyl methacrylate (PFHEMA), 2- (Per Polyfluoroalkyl (meth) acrylates such as fluorobutyl) ethyl methacrylate (PFBEMA); α-fluorostyrene, β-fluorostyrene, α, β-difluorostyrene, β, β-difluorostyrene α, β, β-trifluorostyrene, α-trifluoromethylstyrene, 2,4,6-trifluoro (trifluoromethyl) styrene, 2,3,4,5,6-pentafluorostyrene, 2,3,4 , 5,6-pentafluoro-α-methylstyrene, 2,3,4,5,6-pentafluoro-β-methylstyrene and the like.

When the resin (b) is a urethane resin, the dispersion stabilizer (E) is preferably a urethane resin having a monomer having at least one of a dimethylsiloxane group and a functional group containing fluorine as a structural unit. .
(M1-1) is preferably a polysiloxane having a functional group containing active hydrogen, such as amino-modified silicone, carboxyl-modified silicone, carbinol-modified silicone, or mercapto-modified silicone. (M1-2) includes 2,2-bis (4-hydroxyphenyl) hexafluoropropane, fluorine-containing group polyols such as 3,3,4,4-tetrafluoro-1,6-hexanediol, fluorine-containing groups ( Fluorine compound having a functional group containing active hydrogen such as poly) amine, fluorine-containing group (poly) thiol, bis (isocyanatomethyl) perfluoropropane, bis (isocyanatomethyl) perfluorobutane, bis (isocyanatomethyl) Fluorine-containing (poly) isocyanates such as perfluoropentane and bis (isocyanatomethyl) perfluorohexane are preferred.

  When the resin (b) has an acid value, the dispersion stabilizer (E) preferably has an amino group from the viewpoint of dispersibility. The acid value of the resin (b) is preferably 1 to 50, more preferably 3 to 40, and most preferably 5 to 30. The amino group may be primary, secondary, or tertiary, and is introduced at any position on the side chain, one end, both ends, or both ends of the side chain of a compound containing a fluorine-containing group or a dimethylsiloxane group. May be used.

  As the dispersion stabilizer (E), for example, a monomer (or reactive oligomer) having a dimethylsiloxane group (M1-1) and / or a monomer (M1-2) containing fluorine, and the resin (b) described above are used. A copolymer with a constituting monomer (for example, a copolymer of methacryl-modified silicone and methyl methacrylate, a copolymer of heptafluorobutyl methacrylate and methyl methacrylate, or the like) is preferable. The form of copolymerization may be random, block or graft, but block or graft is preferred.

  When the resin (b) has an acid value, the fine particles (A) preferably have an amino group on the particle surface from the viewpoint of dispersion stability. The amino group may be primary, secondary, or tertiary, and the form in which the amino group is incorporated is not particularly limited. For example, a compound having an amino group is contained in the fine particles (A) by a method such as dispersion or impregnation. A method of using a compound having an amino group as a component constituting the fine particles (A), a method of reacting an amino group-containing coupling agent on the surface of the fine particles (A), an amino group-containing compound on the surfaces of the fine particles (A) And the like.

The addition amount of the dispersion stabilizer (E) is preferably from 0.01 to 50%, more preferably from 0.02 to 40%, particularly preferably from 0.02% to the weight of the resin (b) from the viewpoint of dispersion stability. 03 to 30%. The range of the preferable weight average molecular weight of a dispersion stabilizer (E) is 100-100,000, More preferably, it is 200-50,000, Most preferably, it is 500-30,000. Within this range, the dispersion stabilizing effect of (E) is improved.
In addition, also in manufacturing method (2), (3) and (4), a dispersion stabilizer (E) can be used at a dispersion | distribution process.

  In the present invention, any method may be used to disperse the fine particles (A) in carbon dioxide (X). For example, (A) and (X) are charged in a container, and (A ) Directly in (X), and a method in which a dispersion in which fine particles (A) are dispersed in a solvent (T) is introduced into (X).

  The weight ratio of the fine particles (A) to the weight of carbon dioxide (X) is preferably 50% or less, more preferably 30% or less, and particularly preferably 0.1 to 20%. If it is this range, a resin particle (C1) can be manufactured efficiently.

  Examples of the solvent (T) include the same solvent (S). In view of the dispersibility of the fine particles (A), an aliphatic hydrocarbon solvent (decane, hexane, heptane, etc.) and an ester solvent (ethyl acetate, butyl acetate, etc.) are preferable.

  The weight ratio of the fine particles (A) to the solvent (T) is not particularly limited, but the fine particles (A) are preferably 50% or less, more preferably 30% or less, and particularly preferably with respect to the solvent (T). Is 20% or less. Within this range, the fine particles (A) can be efficiently introduced into (X).

  The method of dispersing the fine particles (A) in the solvent (T) is not particularly limited, but the fine particles (A) are charged into the solvent (T) and directly dispersed by stirring, ultrasonic irradiation, or the like. And crystallization by dissolving in a solvent (T).

  In this manner, a dispersion (X0) in which (A) is dispersed in carbon dioxide (X) is obtained. The fine particles (A) are preferably those that do not dissolve in (X) and are stably dispersed in (X).

  Since the solution (L) of the resin (b) is dispersed in (X), it preferably has an appropriate viscosity. From the viewpoint of particle size distribution, it is preferably 100 Pa · s or less, more preferably 10 Pa · s or less. is there. The solubility of the resin (b) in (X) is preferably 3% or less, more preferably 1% or less.

  The SP value of the resin (b) is preferably 8 to 16, more preferably 9 to 14.

  In the resin particles (B) containing the resin (b) in the present invention, other additives (pigments, fillers, antistatic agents, colorants, release agents, charge control agents, ultraviolet absorbers, antioxidants, An anti-blocking agent, a heat-resistant stabilizer, a flame retardant, etc.) may be contained. As a method for incorporating other additives into the resin particles (B), it is preferable to mix the resin (b) and the additives in advance and then add and disperse the mixture in (X).

  In the present invention, the solution (L) of the resin (b), the solution (L0) of the precursor (b0) of the resin (b) or the precursor (b0) of the resin (b) is added to the fine particles (A Any method may be used as the method of dispersing in the dispersion (X0) in which) is dispersed. As a specific example, the solution (L) of the resin (b), the solution (L0) of the precursor (b0) of the resin (b), or the precursor (b0) of the resin (b) is dispersed with a stirrer or a disperser. A resin (b) solution (L), a resin (b) precursor (b0) solution (L0), or a resin (b) precursor (b0) in liquid or supercritical carbon dioxide ( (X) A method in which the dispersion (X0) in which (A) is dispersed is sprayed through a spray nozzle to form droplets, the resin in the droplets is supersaturated, and the resin particles are precipitated ( ASES: known as Aerosol Solvent Extraction System), coaxial multiple tube (double tube, triple tube, etc.) to solution (L), solution (L0), precursor of resin (b) (b0), dispersion Body (X0) with high pressure gas, entrainer, etc. Examples include a method in which particles are obtained by simultaneously ejecting from a tube and applying external stress to the droplets to promote fragmentation to obtain particles (known as SEDS: Solution Enhanced Dispersion by Supercritical Fluids), a method of irradiating ultrasonic waves, and the like. . The same applies to the solution (L0) of the precursor (b0) of the resin (b) and the precursor (b0) of the resin (b) in the production methods (3) and (2).

In this way, while dispersing the solution (L) of the resin (b) in the dispersion (X0) in which (A) is dispersed in carbon dioxide (X) and adsorbing the fine particles (A) on the surface, By growing particles of the dispersed resin (b), resin particles (C1) in which the fine particles (A) are fixed to the surface of the resin particles (B1) containing the resin (b) and the solvent (S) are formed. A dispersion in which (C1) is dispersed in (X) is referred to as dispersion (X1).
The dispersion (X1) is preferably a single phase. That is, when the resin (b) solution (L) is used, it is not preferable that the solvent (S) phase is separated in addition to the phase containing carbon dioxide (X) in which (C1) is dispersed. Therefore, it is preferable to set the amount of the solution (L) of (b) with respect to the dispersion (X0) so that the solvent phase is not separated. For example, 90% or less is preferable with respect to (X0), more preferably 5 to 80%, and particularly preferably 10 to 70%.
In addition, when the solution (L) of the resin (b) or the solution (L0) of the precursor (b0) of the production method (3) is used, resin particles containing the resin (b) and the solvent (S) ( The amount of (S) contained in B1) is preferably 10 to 90%, more preferably 20 to 70%.
The weight ratio of the resin (b) to carbon dioxide (X) is preferably (b) :( X) is 1: (0.1-100), more preferably 1: (0.5-50). Especially preferably, it is 1: (1-20). The same applies to the weight ratio of the precursor (b0) to carbon dioxide (X) in the production methods (2) and (3).

  In the present invention, liquid carbon dioxide refers to the triple point of carbon dioxide (temperature = −57 ° C., pressure = 0.5 MPa) and the criticality of carbon dioxide on the phase diagram represented by the temperature axis and pressure axis of carbon dioxide. It represents carbon dioxide, which is the temperature / pressure condition of the part surrounded by the gas-liquid boundary line passing through the point (temperature = 31 ° C., pressure = 7.4 MPa), the isotherm of the critical temperature, and the solid-liquid boundary line, and is supercritical The carbon dioxide in the state represents carbon dioxide which is a temperature / pressure condition higher than the critical temperature (however, the pressure represents the total pressure in the case of a mixed gas of two or more components).

  In the production method (1) of the present invention, the operation performed in carbon dioxide (X) is preferably performed at the temperature described below. That is, in order to prevent carbon dioxide from undergoing a phase transition into a solid in the pipe during decompression and block the flow path, the temperature is preferably 30 ° C. or higher, and the fine particles (A), the resin particles (B1), and the resin particles (C1 ) Is preferably 200 ° C. or lower. Furthermore, 30-150 degreeC is preferable, More preferably, it is 34-130 degreeC, Especially preferably, it is 35-100 degreeC, Most preferably, it is 40-80 degreeC. The same applies to the temperature of the dispersion (X0) and the dispersion (X1). The same applies to the manufacturing methods (2) and (3). In the production methods (1) to (3) of the present invention, the operation carried out in carbon dioxide (X) can be carried out at a temperature above or below the Tg or melting point of the fine particles (A). It is preferable to carry out at a temperature below.

  In the production method (1) of the present invention, the operation performed in carbon dioxide (X) is preferably performed at the pressure described below. That is, in order to satisfactorily disperse the resin particles (C1) in (X), it is preferably 7 MPa or more, and preferably 40 MPa or less from the viewpoint of equipment cost and operation cost. More preferably, it is 7.5-35 MPa, More preferably, it is 8-30 MPa, Most preferably, it is 8.5-25 MPa, Most preferably, it is 9-20 MPa. The same applies to the pressure in the container forming the dispersion (X0) and the dispersion (X1). The same applies to the manufacturing methods (2) and (3).

  In the production method (1) of the present invention, the temperature and pressure of the operation performed in carbon dioxide (X) are such that resin (b) does not dissolve in (X) and (b) can be aggregated and united. It is preferable to set within the range. Usually, the target dispersion tends to not dissolve in (X) at lower temperatures and lower pressures, and (b) tends to aggregate and coalesce at higher temperatures and pressures. The same applies to the dispersion (X0) and the dispersion (X1). The same applies to the manufacturing methods (2) and (3).

  In the carbon dioxide (X) in the present invention, other substances (e) may be appropriately contained in order to adjust physical property values (viscosity, diffusion coefficient, dielectric constant, solubility, interfacial tension, etc.) as a dispersion medium. Examples thereof include inert gases such as nitrogen, helium, argon, and air.

  In the present invention, the weight fraction of carbon dioxide (X) in the total of (X) and the other substance (e) is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.

  From the dispersion (X1) in which the resin particles (C1) are dispersed, carbon dioxide (X) is usually removed under reduced pressure to obtain the resin particles (C) of the present invention. At that time, the pressure may be reduced stepwise by providing independent pressure-controlled containers in multiple stages, or may be reduced to normal temperature and normal pressure at a stretch. The method of collecting the obtained resin particles is not particularly limited, and examples thereof include a method of filtering with a filter and a method of centrifuging with a cyclone or the like. The resin particles may be collected after depressurization, or once collected under high pressure before depressurization, and then depressurized. As a method of taking out resin particles from high pressure when collecting under high pressure and then depressurizing, the collection container may be depressurized by batch operation, and continuous extraction operation is performed using a rotary valve. May be.

  After forming the resin particles (C1), if necessary, as a further step, the crystalline resin (a) preferably has a melting point minus 50 ° C. or more, more preferably a melting point minus 10 ° C. or more, and more preferably a melting point. By heating to the above, the fine particles (A) adhering to the surface of the resin particles (B) are melted, and the fine particles (A) are fixed to the surfaces of the resin particles (B), or the film derived from the fine particles (A) The step of forming the resin particles (C1 ′) can also be performed. From the viewpoint of suppressing the aggregation of (C1 ′), the heating time is preferably 0.01 to 1 hour, and more preferably 0.05 to 0.7 hour.

In the resin particles (C) of the present invention obtained by the production methods (1) to (4) of the present invention, the fine particles (A) are once fixed on the surface of the resin particles (B) or (B1). Depending on the composition of the resin (a) and the resin (b) and the type of the solvent (S) or (T), the fine particles (A) are formed into a film during the production process, and (A) is formed on the surface of (B). In some cases, a film is formed.
The resin particles (C) of the present invention are those in which fine particles (A) are fixed on the surface of the resin particles (B), in which a film derived from (A) is formed, and a part of (A) is formed into a film Any of the above may be used.
In addition, the surface state and shape of the resin particle (C) of the present invention can be observed by, for example, a photograph obtained by enlarging the surface of the resin particle 10,000 times or 30,000 times using a scanning electron microscope (SEM).

  After forming the resin particles (C1), it is preferable to perform a step of removing or reducing the solvent (S) as a further step as necessary. That is, when (C1) contains the solvent (S) in the dispersion (X1) dispersed in (X), when the container is decompressed as it is, the solvent dissolved in (X1) condenses and resin particles ( In some cases, C1) may be redissolved or the resin particles (C1) may be joined together when the resin particles (C1) are collected. As a method for removing or reducing the solvent, for example, carbon dioxide (X) is further mixed with the dispersion (X1) obtained by dispersing the solution (L) of the solvent (S) of the resin (b). The solvent (S) is extracted from the resin particles (C1) into the carbon dioxide (X) phase, and then the (X) containing the solvent (S) is replaced with (X) containing no solvent (S), and then It is preferable to reduce the pressure.

  In the mixing method of the dispersion (X1) in which the resin particles (C1) are dispersed in carbon dioxide (X) and (X), (X) having a pressure higher than (X1) may be applied. Although it may be added to (X) at a lower pressure than (X1), the latter is more preferable from the viewpoint of ease of continuous operation. The amount of (X) to be mixed with (X1) is preferably 1 to 50 times the volume of (X1), more preferably 1 to 40 times, most preferably from the viewpoint of preventing coalescence of the resin particles (C1). 1 to 30 times. By removing or reducing the solvent contained in the resin particles (C1) as described above, and then removing (X), it is possible to prevent the resin particles (C1) from being combined.

  As a method of replacing carbon dioxide (X) containing the solvent (S) with (X) not containing the solvent (S), the resin particles (C1) are once supplemented with a filter or cyclone, and then the solvent is maintained while maintaining the pressure. A method of circulating carbon dioxide (X) until (S) is completely removed can be mentioned. The amount of (X) to be circulated is preferably 1 to 100 times, more preferably 1 to 50 times, most preferably 1 to 1 times the volume of (X1) from the viewpoint of solvent removal from the dispersion (X1). 30 times.

  The crystalline resin (a) is preferably heated at a melting point minus 50 ° C. or higher, more preferably at a melting point minus 10 ° C. or higher, and more preferably at a melting point or higher. In the case of performing the above-described step of removing or reducing (), the same as above except that (C1) is changed to (C1 ′).

Next, the production method (2) will be described in detail.
In the present invention, the precursor (b0) of the resin (b) is not particularly limited as long as it can be converted into the resin (b) by a chemical reaction. For example, when the resin (b) is a vinyl resin, Examples of (b0) include the vinyl monomers described above (which may be used alone or in combination), and the resin (b) is a condensation resin (for example, polyurethane resin, epoxy resin, polyester resin). In this case, (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), (b0) may contain a commonly used initiator. Examples of the initiator include peroxide polymerization initiator (I) and azo polymerization initiator (II). Further, the redox polymerization initiator (III) may be formed by using the peroxide polymerization initiator (I) and the 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, etc. (I-2) water-soluble peroxide polymerization initiator: hydrogen peroxide , Peracetic acid, ammonium persulfate, sodium persulfate and the like.

(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: azo Examples thereof include bisamidinopropane salt, azobiscyanovaleric acid (salt), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], and the like.
(III) Redox polymerization initiator: (III-1) Non-aqueous redox polymerization initiator: oil-soluble peroxide such as hydroperoxide, dialkyl peroxide, diacyl peroxide, tertiary amine, naphthenate, mercaptan , Combined use with oil-soluble reducing agents such as organometallic compounds (triethylaluminum, triethylboron, diethylzinc, etc.), (III-2) aqueous redox polymerization initiators: persulfate, hydrogen peroxide, hydroperoxide, etc. Examples thereof include combined use of a water-soluble peroxide and a water-soluble inorganic or organic reducing agent (divalent iron salt, sodium hydrogen sulfite, alcohol, polyamine, etc.).

  When the initiator is used, it is preferable to mix with the monomer in advance before dispersing (b0) in carbon dioxide (X). The polymerization temperature is preferably 40 to 100 ° C, more preferably 60 to 90 ° C.

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). 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). The combination.
(2) A combination in which 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. .

  In the combination (1), the functional group (α1) capable of reacting with the active hydrogen compound includes 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.]; C1-20 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). Among these, (αx), (αy) and (αz) are preferable, and (αx) and (αz) are particularly preferable. 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 incorporating a reactive group into polyester (αx), epoxy resin (αy), polyurethane (αz), etc., (1): by using one of two or more components in excess, A method of leaving a functional group at the end, (2): by using one of two or more constituent components in excess, the functional group of the constituent component can be left at the end and further reacted with the remaining functional group Examples include a method of reacting a compound containing a functional group and a reactive group. 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 component is preferably 2 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. / 1-1 / 1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1. In the case of prepolymers having other skeletons and other end groups, the ratios are the same except that the constituent components are changed. In the said method (2), an isocyanate group containing prepolymer is obtained by making polyisocyanate react with the preprimer obtained by the said method (1), and blocked isocyanate group containing prepolymer is made to react with blocked polyisocyanate. 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 an 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 preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, particularly preferably 2.5 /. 1 to 1.5 / 1. In the case of prepolymers having other skeletons and other end groups, the ratios are 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 said range, the molecular weight of the hardened | cured material obtained by making it react with a hardening | curing agent ((beta)) becomes high. The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000. The weight average molecular weight of the reactive group-containing prepolymer (α) is 1,000 to 50,000, preferably 2,000 to 40,000, and more preferably 4,000 to 20,000. The viscosity of the reactive group-containing prepolymer (α) is preferably 2,000 poise or less, more preferably 1,000 poise or less 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. Of these, (β1a), (β1b) and (β1d) are preferred, (β1a) and (β1d) are more preferred, and particularly preferred are blocked polyamines (β1a) and (Β1d). (Β1a) is exemplified by those similar to polyamine (16). Preferred as (β1a) are 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine 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) And phenol; monomercaptan (such as butyl mercaptan and lauryl mercaptan); monoisocyanate (such as lauryl isocyanate and phenyl isocyanate); monoepoxide (such as butyl glycidyl ether) and the like.

  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 an 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 same as the dicarboxylic acid (13), and examples of the polycarboxylic acid include the polycarboxylic acid (14), and preferable examples thereof 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 preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and particularly preferably 1.2 / 1 to 1 / 1.2. When the curing agent (β) is water (β1d), water is treated as a divalent active hydrogen compound.

  When the combination of the prepolymer (α) having a reactive group and the curing agent (β) is used as the precursor (b0), in the dispersion (X0) in which the fine particles (A) are dispersed in carbon dioxide (X) The method of reacting (b0) is not particularly limited, but a method of mixing (α) and (β) immediately before dispersing (b0) in (X0) and reacting at the same time as dispersing is preferred. Although reaction time is selected by the reactivity by the structure of the reactive group which prepolymer ((alpha) has), and the combination of a hardening | curing agent ((beta)), Preferably it is 5 minutes-24 hours. The reaction may be completed in (X0) before depressurization, or may be allowed to react to some extent at (X0), depressurized and (C) is taken out, and then aged in a thermostatic bath or the like to be completed. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate in the case of reaction of an isocyanate and an active hydrogen compound. The reaction temperature is preferably 30 to 100 ° C, more preferably 40 to 80 ° C.

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

Further, when the reactive group-containing prepolymer (α) and the curing agent (β) are reacted, a reactive group-containing prepolymer (α) and a polymer that does not react with the curing agent (β) [so-called dead polymer] are incorporated in the system. It can also be contained. In this case, (b) is a mixture of a resin obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) and an unreacted resin.
In the case of the production method (2), the above-mentioned matters and the precursor during dispersion using the precursor (b0) of the resin (b) instead of the solution (L) obtained by dissolving the resin (b) in the solvent (S) Except for reacting (b0), this is the same as Production Method (1).

The production method (3) will be described in detail.
Instead of the solvent (S) solution (L) of the resin (b), the solvent (S) solution (L0) of the precursor (b0) of the resin (b) is used to react the precursor (b0) during dispersion. Except for this, it is the same as the manufacturing method (1).

  The production method (4) will be described in detail.

  In the fifth invention, any method may be used for dispersing the fine particles (A) in the non-aqueous organic solvent (N). For example, (A) and (N) are charged in a container, stirring, spraying, ultrasonic Examples thereof include a method in which (A) is directly dispersed in (N) by irradiation and a method in which the solvent dispersion in (A) is introduced into (N). The fine particles (A) are preferably those that do not dissolve in (N) and are stably dispersed in (N).

The non-aqueous organic solvent (N) used in the fifth invention is preferably an organic solvent having a solubility of the resin (b) of 1% or less among the organic solvent (S1) described later. If the solubility of the resin (b) is 1% or less, it is preferable that the resin particles (C) are difficult to unite with each other. The solubility of the resin (b) in the non-aqueous organic solvent (N) is determined from the non-aqueous dispersion containing the insoluble component (b) in which (b) is dissolved in (N) until saturation is reached. The weight of the supernatant obtained by sedimentation of the dissolved component by centrifugation, and the weight of the residue after drying at the boiling point of the non-aqueous organic solvent (N) with a vacuum dryer is taken as the value.
Specifically, it is calculated by the following procedure.
The non-aqueous dispersion (25 ° C.) is centrifuged at 3000 rpm for 10 minutes, and about 2 g (wg) of the supernatant is collected in an aluminum container. Further, the supernatant is dried with a vacuum dryer under a reduced pressure of 20 mmHg for 1 hour under the temperature condition of the boiling point of the non-aqueous organic solvent (N), and the weight of the residue is weighed. If the weight of the residue at this time is Wg, the solubility of the resin (b) in the non-aqueous organic solvent (N) can be calculated by W / w × 100 [%].
Specifically, the non-aqueous organic solvent (N) is preferably a hydrocarbon solvent (hexane, octane, decane, dodecane, isododecane, liquid paraffin, etc.) and silicone oil.

The solubility parameter (SP value) of the organic solvent (S1) is preferably in the range of 9.5 to 20, and more preferably 10 to 19. When the SP value of the organic solvent (S1) is within this range, the organic solvent (S1) solution of the resin (b) or the organic solvent (S1) solution of the precursor (b0) of the resin (b) is non-aqueous organic. When dispersed in the solvent (N), (S1) is not extracted into (N), and the particle size distribution of the resin particles (C) is preferably not widened.
When a mixed solvent is used as the organic solvent (S1), the SP value is assumed to satisfy the additivity rule, and the average value calculated from the SP value of each solvent is preferably within the above range.

  As the organic solvent (S1), those suitable for the combination with the resin (b) or the precursor (b0) of the resin (b) within the above range can be appropriately selected, and toluene, xylene, ethylbenzene, tetralin, etc. Aromatic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirits, cyclohexane and other aliphatic or alicyclic hydrocarbon solvents; methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride Halogen solvents such as trichloroethylene and perchloroethylene; ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate; diethyl ether, tetrahydrofuran (hereinafter referred to as THF) .), Dioxane, Ethi Ether solvents such as cellosolve, butyl cellosolve, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, iso Alcohol solvents such as butanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol; Amide solvents such as dimethylformamide and dimethylacetamide; Sulfoxide solvents such as dimethyl sulfoxide; Heterocyclic compound solvents such as N-methylpyrrolidone As well as a mixed solvent of two or more of these.

  For example, when polyester, polyurethane, or epoxy resin is selected as the resin (b), preferable organic solvents (S1) include acetone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and a mixed solvent of two or more of these. Can do.

  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) is And the above-mentioned vinyl monomers (which may be used alone or in combination), and when 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). The details are the same as in manufacturing method (2).

  Any method may be used for dissolving the resin (b) or the precursor (b0) of the resin (b) in the organic solvent (S1), and a known method can be used. For example, in the organic solvent (S1) Examples thereof include a method in which the resin (b) or the precursor (b0) is charged and stirred, and a method in which heating is performed.

Since the organic solvent (S1) solution of the resin (b) or the precursor (b0) is dispersed in (N), it preferably has an appropriate viscosity, and is preferably 100 Pa · s or less from the viewpoint of particle size distribution. The pressure is preferably 10 Pa · s or less.
The SP value of the resin (b) is preferably 8 to 16, more preferably 9 to 14.

  In the production method of the fifth invention, the organic solvent (S1) solution of the resin (b), the organic solvent (S1) solution of the precursor (b0) of the resin (b), and a mixture thereof, other additions Agents (colorants, mold release agents, charge control agents, antioxidants, anti-blocking agents, heat stabilizers, fluidizing agents, etc.) can be mixed.

  In the production method of the fifth invention, the dispersion in which the fine particles (A) are dispersed in the non-aqueous organic solvent (N), and the resin (b) or the precursor (b0) of the resin (b) are mixed with the organic solvent ( The solution dissolved in S1) is mixed, the organic solvent (S1) solution is dispersed in the non-aqueous dispersion of (A), and (b0) is reacted if necessary, in the dispersion of (A) By forming the resin particles (B) containing the resin (b), a non-aqueous dispersion of the resin particles (C2) having a structure in which the fine particles (A) are fixed to the surfaces of the resin particles (B) is obtained. .

  The amount of the fine particle (A) dispersion used for 100 parts by weight of the resin (b) is preferably 50 to 2000 parts by weight, more preferably 100 to 1000 parts by weight. If it is 50 parts by weight or more, the dispersed state of (b) is good, and if it is 2000 parts by weight or less, it is economical.

When the organic solvent (S1) solution of the resin (b) or the precursor (b0) is dispersed in the non-aqueous dispersion of the fine particles (A), a dispersing device can be used.
The dispersion apparatus used in the production method (4) is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. Specific examples thereof include those described in JP-A-2002-284881. It is done.

As a method of removing the organic solvent (S1) and the non-aqueous organic solvent (N) from the non-aqueous dispersion of the resin particles (C2) to obtain the resin particles (C),
[1] Method of drying organic solvent (S1) and non-aqueous organic solvent (N) under reduced pressure or normal pressure [2] Solid-liquid separation with a centrifuge, a spatula filter, a filter press, etc. Method of drying [3] Method of freezing and drying organic solvent (S1) and non-aqueous organic solvent (N) (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 using an air classifier etc. as needed, and can also be made into a predetermined particle size distribution.
During the manufacturing process such as the drying process, the fine particles (A) containing the crystalline resin (a) are formed into a film, and a film containing (a) is formed on the surface of the resin particles (B). There is a case.

  According to the said manufacturing method (1)-(4), the resin particle (C) of this invention which does not contain the surfactant which has a hydrophilic group substantially can be manufactured. Here, the surfactant having a hydrophilic group is an anionic surfactant (s-1), a cationic surfactant (s-2), an amphoteric surfactant (s-3), a nonionic surfactant ( s-4). Examples of the anionic surfactant (s-1) include carboxylic acids or salts thereof, sulfate esters, carboxymethylated salts, sulfonates and phosphate esters. Examples of the cationic surfactant (s-2) include quaternary ammonium salt type surfactants and amine salt type surfactants. Examples of the amphoteric surfactant (s-3) include a carboxylate amphoteric surfactant, a sulfate ester amphoteric surfactant, a sulfonate amphoteric surfactant, and a phosphate ester amphoteric surfactant. Can be mentioned. Examples of the nonionic surfactant (s-4) include an AO addition type nonionic surfactant and a polyvalent alcohol type nonionic surfactant.

  Specific examples of these surfactants include those described in International Publication WO 03/106541. Usually, resin particles produced using a surfactant having a hydrophilic group in an aqueous solvent substantially contain a surfactant having a hydrophilic group.

As a method for analyzing that the resin particles do not substantially contain a surfactant having a hydrophilic group, a known surface wettability evaluation (Color Material Association, No. 73 [3], 2000, P132 to 138). ). The surface wettability evaluation method is as follows. That is, 0.1 g of resin particles are put into a 100 ml beaker, 20 ml of ion-exchanged water is added thereto, the mixture is stirred with a magnetic stirrer, and the resin particles are floated on the liquid surface. The weight of acetone (Wa) and the weight of water (Ww) are eliminated with three significant figures, and the solubility parameter (δm) on the surface of the resin particles is calculated from the equation (1).
δm = (9.75 × Wa + 23.43 × Ww) / (Wa + Ww) (1)

  If the solubility parameter (δm) on the surface of the resin particle is 9.8 to 21, preferably 9.8 to 20, it is judged that the resin particle does not substantially contain a surfactant having a hydrophilic group. . When δm is 9.8 to 21, the moisture resistance storage stability of the resin particles is good, and the electrical characteristics, fluidity, and fixability under high humidity are good. This measurement method cannot measure less than 9.8.

The resin particle (C) of the present invention changes the particle size of the fine particles (A) and the resin particles (B) and the coverage of the surface of the resin particles (B) with the coating derived from the fine particles (A) or (A). Thus, desired irregularities can be imparted to the particle surface. Furthermore, by controlling the temperature and pressure during decompression, a porous body having bubbles inside can be obtained, and the specific surface area can be increased. When it is desired to improve the powder fluidity, the resin particles preferably have a BET specific surface area of 0.5 to 5.0 m ² / g. The BET specific surface area is measured using a specific surface area meter such as QUANTASORB (manufactured by Yuasa Ionics) (measurement gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen). Similarly, from the viewpoint of powder fluidity, the surface average center line roughness Ra of the resin particles (C) of the present invention 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 resin particles (C) of the present invention obtained by the production method of the present invention have a sharp particle size distribution and are usually hydrophobic because they do not contain a water-soluble surfactant or ionic substance. Accordingly, the resin particles (C) of the present invention are used for electrophotographic toners, paint additives, adhesive additives, cosmetic additives, paper coating additives, slush molding resins, powder coatings, and electronic component manufacturing. It is useful as a spacer for a catalyst, a carrier for a catalyst, an electrostatic recording toner, an electrostatic printing toner, a standard particle for an electronic measuring instrument, a particle for an electronic paper, a carrier for a medical diagnosis, a chromatographic filler, a particle for an electrorheological fluid.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following description, “parts” indicates parts by weight.

The following crystallinity, Mn, melting point, glass transition temperature, and volume average particle diameter were measured by the following methods.
<Measurement method of crystallinity>
A sample (5 mg) was collected and placed in an aluminum pan, and the temperature was increased from room temperature to a temperature increase rate of 20 ° C./min using DSC (differential scanning calorimetry) (measuring device: RDC220, manufactured by SII Nano Technology Co., Ltd.). The amount of heat of fusion (ΔHm (J / g)) determined from the area of the endothermic peak was determined while changing. Based on the measured ΔHm, the degree of crystallinity (%) was calculated by the following formula.
Crystallinity = (Heat of fusion / a) × 100
In the above formula, a is measured as follows.
Measurement method according to JISK0131 (1996) (X-ray diffraction analysis general rule 13 crystallinity measurement (2) absolute method) by measuring the heat of fusion of a resin having the same composition as the resin to be measured by DSC Measure the crystallinity at When the heat of fusion is plotted on the vertical axis and the crystallinity is plotted on the horizontal axis, the standard data is plotted, and a straight line is drawn from the two points of that point and the origin, and extrapolated so that the crystallinity is 100% The value obtained by calculating the amount of heat of fusion is a.

<Measuring method of number average molecular weight (Mn)>
Each sample was dissolved in tetrahydrofuran at a concentration of 2.5 g / L and measured by GPC using polystyrene as a standard substance.
GPC model: HLC-8120GPC, manufactured by Tosoh Corporation Column: 2 TSKgel GMHXL) + TSKgel Multipore HXL-M (made by Tosoh Corporation)
<Measuring method of melting point>
A sample (5 mg) is collected and placed in an aluminum pan, and the DSC (Differential Scanning Calorimetry) (measuring device: RDC220, manufactured by SII NanoTechnology Co., Ltd.) is used to absorb heat by crystal melting at a heating rate of 10 ° C./min. The peak temperature (° C.) was determined.
<Measuring method of glass transition temperature (Tg)>
5 mg of each sample was weighed, and the glass transition temperature was measured at a heating rate of 10 ° C. per minute by DSC (Differential Scanning Calorimetry) (measuring device: RDC220, manufactured by SII Nano Technology Co., Ltd.).
<Measurement method of volume average particle diameter>
After 5 mg of the sample was dispersed in 10 g of ion-exchanged water, measurement was performed with Multisizer III (manufactured by Coulter).

Production Example 1 <Preparation of Resin (b-1)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 831 parts of 1,2-propylene glycol (hereinafter referred to as propylene glycol), 703 parts of terephthalic acid, 47 parts of adipic acid, and tetrabutoxy as a condensation catalyst 0.5 part of titanate was added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the water produced. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 5 to 20 mmHg, and the softening point becomes 87 ° C. After cooling to 180 ° C., 24 parts of trimellitic anhydride and 0.5 part of tetrabutoxy titanate were added, reacted for 90 minutes, and then taken out. The recovered propylene glycol was 442 parts. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a polyester resin (b-1). This resin had Mn of 1900 and Tg of 45 ° C.

Production Example 2 <Preparation of Resin (b-2)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 729 parts of propylene glycol, 683 parts of terephthalic acid, 67 parts of adipic acid, 38 parts of trimellitic anhydride and 0.5 part of tetrabutoxy titanate as a condensation catalyst The mixture was allowed to react for 8 hours at 180 ° C. while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was carried out for 4 hours while distilling off the propylene glycol and water produced under a nitrogen stream, and the reaction was further carried out under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 172 parts. When the softening point reached 160 ° C., it was taken out, cooled to room temperature, pulverized and granulated to obtain a polyester resin (b-2). This resin had Mn of 5700 and Tg of 63 ° C.

Production Example 3 <Preparation of Resin (b-3)>
24 parts of xylene was charged into an autoclave equipped with a stir bar and a thermometer, and mixed monomer 2 of butyl acrylate / methyl methacrylate / styrene / 2-ethylhexyl acrylate (25% / 33% / 40% / 2%) 1,000 parts and 1 part of the polymerization catalyst were dropped at 170 ° C. over 3 hours. Volatilization was performed at normal pressure while raising the temperature to 180 ° C., and when the temperature reached 180 ° C., the pressure was switched to reduced pressure, and devolatilization was performed over 2 hours to obtain a vinyl resin (b-3). This resin had Mn of 10,500 and Tg of 62 ° C.

Production Example 4 <Preparation of Resin Solution (L-1)>
In a container equipped with a stirrer, 228 parts of resin (b-1) obtained in Production Example 1 was added to solvent (S-1), which is a mixed solvent consisting of 490 parts of acetone, 175 parts of methanol, and 35 parts of ion-exchanged water. And 57 parts of the resin (b-2) obtained in Production Example 2, were stirred until the resin (b-1) and the resin (b-2) were completely dissolved, and the resin solution (L-1) was added. Obtained. The solvent (S-1) has a weight of insoluble matter of the resin (b) of 0.1% or less with respect to the weight of the resin (b) in the equal weight mixture of the resin (b) and the solvent (S-1) in the standard state. The SP value of (S-1) was 11.8.

Production Example 5 <Preparation of Resin Solution (L-2)>
In a container equipped with a stirrer, 228 parts of the resin (b-1) obtained in Production Example 1 in the solvent (S-2), which is a mixed solvent consisting of 450 parts of acetone and 50 parts of ion-exchanged water, and Production Example 57 parts of the resin (b-2) obtained in 2 was charged and stirred until the resins (b-1) and (b-2) were completely dissolved to obtain a resin solution (L-2). Solvent (S-2) is 0.1% or less in weight of insoluble matter of resin (b) relative to the weight of resin (b) in an equal weight mixture of resin (b) and solvent (S-2) in the standard state. The SP value of (S-2) was 11.3.

Production Example 6 <Preparation of Resin Solution (L-3)>
In a container equipped with a stirrer, 280 parts of the resin (b-3) obtained in Production Example 3 and 280 parts of the resin (b-3) obtained in Production Example 3 were charged into a solvent (S-3) consisting of 490 parts of acetone and 210 parts of methanol. Stirring until b-3) was completely dissolved to obtain a resin solution (L-3). The solvent (S-3) has a weight of insoluble matter of the resin (b) of 0.1% or less with respect to the weight of the resin (b) in the equal weight mixture of the resin (b) and the solvent (S-3) in the standard state. The SP value of (S-3) was 11.3.

Production Example 7 <Preparation of Resin Solution (L-4)>
In a vessel equipped with a stirrer, 700 parts of solvent (S-4), which is a mixed solvent composed of 560 parts of acetone, 70 parts of ion-exchanged water, and 70 parts of decane, resin (b-1) 228 obtained in Production Example 1 Part, and 57 parts of the resin (b-2) obtained in Production Example 2, were stirred until the resins (b-1) and (b-2) were completely dissolved, and the resin solution (L-4) was added. Obtained. Solvent (S-4) has a weight of insoluble matter of resin (b) of 0.1% or less with respect to the weight of resin (b) in an equal weight mixture of resin (b) and solvent (S-4) in the standard state. The SP value of (S-4) was 10.3.

Production Example 8 <Preparation of resin precursor (b0-1)>
Into an autoclave, 407 parts of the resin (b-1) obtained in Production Example 1, 54 parts of isophorone diisocyanate (IPDI), and 485 parts of acetone are charged, and the reaction is carried out in a sealed state at 100 ° C. for 5 hours. A resin precursor (b0-1) having a group was obtained. The NCO content of the resin precursor (b0-1) was 0.8%.

Production Example 9 <Adjustment of curing agent (β)>
A curing vessel which is a ketimine compound by removing 50% of isophorone diamine and 300 parts of methyl ethyl ketone in a reaction vessel equipped with a stirrer, a solvent removal device, and a thermometer and reacting at 50 ° C. for 5 hours. (Β) (urethane prepolymer chain extender) was obtained. The total amine value of the curing agent (β) was 415.

Production Example 10 <Preparation of resin precursor solution (L-5)>
In a container equipped with a stirrer, 700 parts of solvent (S-5), which is dimethylformamide, 228 parts of resin (b-1) obtained in Production Example 1, and the resin precursor (b0-) obtained in Production Example 8 1) Charge 57 parts and 1.5 parts of curing agent (β), and stir until the resin precursor (b0-1) and curing agent (β) are completely dissolved to obtain a resin solution (L-5). It was. The solvent (S-5) is based on the weight of the resin (b) and the precursor (b0) in the equal weight mixture of the resin (b) and the precursor (b0) and the solvent (S-5) in the above-mentioned weight ratio in the standard state. The weight of insoluble matter in (b) and (b0) was 0.1% or less, and the SP value of the solvent (S-5) was 12.0.

Production Example 11 <Preparation of Resin Solution (L-6)>
In a container equipped with a stirrer, 490 parts of acetone, 700 parts of solvent (S-6) which is a mixed solvent consisting of 210 parts of ion-exchanged water, 228 parts of resin (b-1) obtained in Production Example 1, and production 57 parts of the resin (b-2) obtained in Example 2 was charged and stirred until the resins (b-1) and (b-2) were completely dissolved to obtain a resin solution (L-6). The solvent (S-6) was a resin (b) having an insoluble weight of 15% with respect to the weight of the resin (b) in an equal weight mixture of the resin (b) and the solvent (S-6) in the standard state. The SP value of 6) was 14.0.

Production Example 12 <Preparation of Crystalline Resin (a-1)>
A reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel, and nitrogen blowing tube was charged with 500 parts of toluene, and another glass beaker was charged with 350 parts of toluene and behenyl acrylate (22 carbon atoms directly). Acrylate of an alcohol having a chain alkyl group: 120 parts of Bremer VA (manufactured by NOF), 22.5 parts of methyl methacrylate, 7.5 parts of (2-perfluorodecyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries), AIBN ( Azobisisobutyronitrile) 10 parts was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting the gas phase portion of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. over 2 hours in a sealed state, and after aging at 85 ° C. for 2 hours from the end of the addition, toluene was added at 130 ° C. for 3 hours. After removing under reduced pressure, a crystalline resin (a-1) was obtained. The crystallinity of this resin was 60%, the melting point was 60 ° C., and Mn was 8,000.

Production Example 13 <Preparation of Fine Particle (A-1) Dispersion>
After mixing 700 parts of normal hexane and 300 parts of crystalline resin (a-1), pulverization was performed using zirconia beads having a particle diameter of 0.3 mm with a bead mill (Dynomill Multilab: manufactured by Shinmaru Enterprises). A milky white fine particle (A-1) dispersion was obtained. The volume average particle size of this dispersion was 0.4 μm.

Production Example 14 <Preparation of Crystalline Resin (a-2)>
Into a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel, and nitrogen blowing tube, 500 parts of toluene was charged, and in another glass beaker, 350 parts of toluene, stearyl acrylate (18 carbon atoms) Acrylate of alcohol having a chain alkyl group: 75 parts of Bremermer SA (manufactured by NOF), 15 parts of 2-hydroxyethyl methacrylate, 29.85 parts of methyl methacrylate, 15 parts of acrylonitrile, 15 parts of methacrylic acid, (2-perfluoro (Butyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries) 0.15 part and AIBN (azobisisobutyronitrile) 2.5 part are charged and stirred and mixed at 20 ° C. to prepare a monomer solution. Prepared. After substituting nitrogen in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 80 ° C. for 2 hours in a sealed state, and after aging at 85 ° C. for 2 hours after completion of the addition, toluene was added at 130 ° C. for 3 hours. After removing under reduced pressure, a crystalline resin (a-2) was obtained. The crystallinity of this resin was 50%, the melting point was 50 ° C., and Mn was 300000.

Production Example 15 <Preparation of Fine Particle (A-2) Dispersion>
In Production Example 13, a milky white fine particle (A-2) dispersion was obtained in the same manner as in Production Example 13 except that the crystalline resin (a-2) was used instead of the crystalline resin (a-1). It was. The volume average particle diameter of this dispersion was 0.3 μm.

Production Example 16 <Preparation of Crystalline Resin (a-3)>
Into a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel, and nitrogen blowing tube, 500 parts of toluene was charged, and another glass beaker was charged with 350 parts of toluene and behenyl acrylate (directly containing 22 carbon atoms). Acrylate of alcohol having a chain alkyl group: 112.5 parts of Blemmer VA (manufactured by NOF), 37.5 parts of 2,2,2-trifluoroethyl acrylate (manufactured by Wako Pure Chemical Industries), AIBN (azobisisobutyro Nitrile) 7.5 parts was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting nitrogen in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 80 ° C. for 2 hours in a sealed state, and after aging at 85 ° C. for 2 hours after completion of the addition, toluene was added at 130 ° C. for 3 hours. After removing under reduced pressure, a crystalline resin (a-3) was obtained. This resin had a crystallinity of 20%, a melting point of 55 ° C., and Mn of 50000.

Production Example 17 <Preparation of Fine Particle (A-3) Dispersion>
In Production Example 13, a milky white fine particle (A-3) dispersion was obtained in the same manner as in Production Example 13, except that the crystalline resin (a-3) was used instead of the crystalline resin (a-1). It was. The volume average particle size of this dispersion was 0.15 μm.

Production Example 18 <Preparation of Crystalline Resin (a-4)>
A reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel, and nitrogen blowing tube was charged with 500 parts of toluene, and another glass beaker was charged with 350 parts of toluene and behenyl acrylate (22 carbon atoms directly). Acrylate of an alcohol having a chain alkyl group: 120 parts of Blemmer VA (manufactured by NOF), 28.5 parts of methyl methacrylate, 1.5 parts of (2-perfluorodecyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries), AIBN ( Azobisisobutyronitrile) 2.5 parts was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting the gas phase portion of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. over 2 hours in a sealed state, and after aging at 85 ° C. for 2 hours from the end of the addition, toluene was added at 130 ° C. for 3 hours. After removing under reduced pressure, a crystalline resin (a-4) was obtained. The crystallinity of this resin was 70%, the melting point was 70 ° C., and Mn was 300,000.

Production Example 19 <Preparation of Fine Particle (A-4) Dispersion>
In Production Example 13, a milky white fine particle (A-4) dispersion was obtained in the same manner as in Production Example 13 except that the crystalline resin (a-4) was used instead of the crystalline resin (a-1). It was. The volume average particle diameter of this dispersion was 0.3 μm.

Production Example 20 <Preparation of Crystalline Resin (a-5)>
Into a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel, and nitrogen blowing tube, 500 parts of toluene was charged, and another glass beaker was charged with 350 parts of toluene and behenyl acrylate (directly containing 22 carbon atoms). 120 parts of acrylate of alcohol having a chain alkyl group: Blemmer VA (manufactured by NOF)), 27 parts of methyl methacrylate, 3 parts of maleic anhydride and 8 parts of AIBN (azobisisobutyronitrile) are stirred at 20 ° C. The monomer solution was prepared by mixing and charged into the dropping funnel. After substituting nitrogen in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 80 ° C. for 2 hours in a sealed state, and after aging at 85 ° C. for 2 hours after completion of the addition, toluene was added at 130 ° C. for 3 hours. After removing under reduced pressure, a crystalline resin (a-5) was obtained. The crystallinity of this resin was 65%, the melting point was 65 ° C., and Mn was 30000.

Production Example 21 <Preparation of Fine Particle (A-5) Dispersion>
In Production Example 13, a milky white fine particle (A-5) dispersion was obtained in the same manner as in Production Example 13 except that the crystalline resin (a-5) was used instead of the crystalline resin (a-1). It was. The volume average particle diameter of this dispersion was 0.3 μm.

Production Example 22 <Preparation of Crystalline Resin (a-6)>
Into a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel, and nitrogen blowing tube, 500 parts of toluene was charged, and another glass beaker was charged with 350 parts of toluene and behenyl acrylate (directly containing 22 carbon atoms). Acrylate of alcohol having a chain alkyl group: 125 parts of Blemmer VA (manufactured by NOF), 18 parts of styrene, 2 parts of (2-perfluorodecyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries), 5 parts of fumaric acid, AIBN (azo) 6 parts of bisisobutyronitrile) was added, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting nitrogen in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 80 ° C. for 2 hours in a sealed state, and after aging at 85 ° C. for 2 hours after completion of the addition, toluene was added at 130 ° C. for 3 hours. After removing under reduced pressure, a crystalline resin (a-6) was obtained. The crystallinity of this resin was 60%, the melting point was 60 ° C., and Mn was 70000.

Production Example 23 <Preparation of Fine Particle (A-6) Dispersion>
In Production Example 13, a milky white fine particle (A-6) dispersion was obtained in the same manner as in Production Example 13 except that the crystalline resin (a-6) was used instead of the crystalline resin (a-1). It was. The volume average particle size of this dispersion was 0.2 μm.

Production Example 24 <Preparation of Dispersion Stabilizer (E) Solution>
700 parts of THF was charged into a reaction vessel equipped with a stirrer, and the air in the reaction vessel was purged with nitrogen, followed by heating to a reflux temperature. Next, 150 parts of methyl methacrylate, 150 parts of methacryl-modified silicone (functional group equivalent: 12,000 g / mol, Mn 12000: X22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd.)), 1.5 parts of azobisisobutyronitrile The mixture was appropriately reduced in the reaction group in 2 hours and then aged at reflux temperature for 6 hours to obtain a dispersion stabilizer (E-1) solution. The weight average molecular weight of (E-1) was 120,000.

Example 1
In the experimental apparatus of FIG. 1, first, the valves V1 and V2 were closed, carbon dioxide (purity 99.99%) was introduced into the particle recovery tank T4 from the cylinder B2 and the pump P4, and the pressure was adjusted to 14 MPa and 40 ° C. The resin solution (L-1) was charged in the resin solution tank T1, and the fine particle (A-1) dispersion was charged in the fine particle dispersion tank T2. Next, carbon dioxide was introduced into the dispersion tank T3 from the cylinder B1 and the pump P3, adjusted to 9 MPa and 40 ° C., and the fine particle (A-1) dispersion was introduced from the tank T2 and the pump P2. Next, the resin solution (L-1) was introduced into the dispersion tank T3 from the tank T1 and the pump P1 while stirring the inside of the dispersion tank T3 at 2000 rpm. After the introduction, the pressure inside T3 was 14 MPa.

The weight ratio of the composition charged into the dispersion tank T3 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-1) dispersion 45 parts Carbon dioxide 550 parts The weight of the introduced carbon dioxide is determined from the temperature of carbon dioxide (40 ° C) and the pressure (15 MPa). The density was calculated from the state equation described in Document 2 below, and was calculated by multiplying this by the volume of the dispersion tank T3.
Reference 2: Journal of Physical and Chemical Reference data, vol. 25, P.I. 1509 to 1596

  After introducing the resin solution (L-1), the mixture was stirred for 1 minute to obtain a dispersion (X1). After opening the valve V1 and introducing carbon dioxide into T4 from P3, the dispersion (X1) was introduced into T4, and the opening degree of V2 was adjusted so that the pressure was kept constant during this time. This operation was performed for 30 seconds, and V1 was closed. By this operation, the solvent was extracted from the resin solution introduced into T4. Further, T4 was heated to 60 ° C. and held for 15 minutes. By this operation, the fine particles (A-1) were fixed to the surface of the resin particles (B-1) formed from the resin solution (L-1), and resin particles (C-1) were generated. Next, carbon dioxide containing the extracted solvent is discharged to the solvent trap tank T5 by holding the pressure at 14 MPa by the pressure adjusting valve V2 while introducing carbon dioxide into the particle recovery tank T4 from the pressure cylinder B2 and the pump P4. At the same time, the resin particles (C-1) were captured by the filter F1. The operation of introducing carbon dioxide into the particle recovery tank T4 from the pressure cylinder B2 and the pump P4 is to introduce carbon dioxide when 5 times the weight of carbon dioxide introduced into the dispersion tank T3 is introduced into the particle recovery tank T4. Stopped. At the time of this stop, the operation of replacing carbon dioxide containing the solvent with carbon dioxide not containing the solvent and capturing the resin particles (C-1) in the filter F1 was completed. Furthermore, the pressure regulating valve V2 is opened little by little, the inside of the particle recovery tank is reduced to atmospheric pressure, and the resin in which the film derived from the fine particles (A) is formed on the surface of the resin particles (B) supplemented by the filter F1. Particles (C-1) were obtained.

Example 2
In Example 1, the fine particle (A-2) dispersion was used instead of the fine particle (A-1) dispersion, and the resin solution (L-2) was used instead of the resin solution (L-1). Except for the above, resin particles (C-2) were obtained in the same manner as in Example 1, in which a film derived from the fine particles (A) was formed on the surface of the resin particles (B). The weight ratio of the composition charged into the dispersion tank T3 in Example 2 is as follows.
Resin solution (L-2) 270 parts Fine particle (A-2) dispersion 45 parts Carbon dioxide 550 parts

Example 3
In Example 1, the fine particle (A-3) dispersion was used instead of the fine particle (A-1) dispersion, and the resin solution (L-3) was used instead of the resin solution (L-1). Except for the above, resin particles (C-3) were obtained in the same manner as in Example 1, in which coatings derived from the fine particles (A) were formed on the surfaces of the resin particles (B). The weight ratio of the composition charged into the dispersion tank T3 in Example 3 is as follows.
Resin solution (L-3) 270 parts Fine particle (A-3) dispersion 45 parts Carbon dioxide 550 parts

Example 4
In Example 1, the fine particle (A-4) dispersion was used instead of the fine particle (A-1) dispersion, and the resin solution (L-4) was used instead of the resin solution (L-1). Except that, resin particles (C-4) in which the fine particles (A) were fixed to the surfaces of the resin particles (B) were obtained in the same manner as in Example 1. The weight ratio of the composition charged into the dispersion tank T3 in Example 4 is as follows.
Resin solution (L-4) 270 parts Fine particle (A-4) dispersion 45 parts Carbon dioxide 550 parts

Example 5
In Example 1, 14 parts of hydrophobic dispersion stabilizer (E-1) was added, and (L-5) was used instead of resin solution (L-1). Resin particles (C-5) in which a film derived from the fine particles (A) was formed on the surfaces of the resin particles (B) were obtained. The weight ratio of the composition charged into the dispersion tank T3 in Example 5 is as follows.
Resin solution (L-5) 270 parts Fine particle (A-1) dispersion 45 parts Dispersion stabilizer (E-1) solution 14 parts Carbon dioxide 550 parts

Example 6
In Example 1, in the same manner as in Example 1 except that the resin solution (L-6) was used instead of the resin solution (L-1), the surface of the resin particle (B) was derived from the fine particles (A). Resin particles (C-6) on which a film was formed were obtained. The weight ratio of the composition charged into the dispersion tank T3 in Example 6 is as follows.
Resin solution (L-6) 270 parts Fine particle (A-1) dispersion 45 parts Carbon dioxide 550 parts

Example 7
In Example 1, the surface of the resin particles (B) was obtained in the same manner as in Example 1 except that the resin precursor (b0-1) and 20 parts of ion-exchanged water were used instead of the resin solution (L-1). The resin particle (C-7) in which the membrane | film | coat derived from microparticles | fine-particles (A) was formed in was obtained. The weight ratio of the composition charged into the dispersion tank T3 in Example 7 is as follows.
Resin precursor (b0-1) 270 parts Ion exchange water (water for ketimine extension) 20 parts Fine particle (A-1) dispersion 45 parts Carbon dioxide 550 parts

Example 8
In Example 1, the fine particle (A-5) dispersion was used instead of the fine particle (A-1) dispersion, and the resin solution (L-2) was used instead of the resin solution (L-1). Except for the above, resin particles (C-8) were obtained in the same manner as in Example 1 in which the coatings derived from the fine particles (A) were formed on the surfaces of the resin particles (B). The weight ratio of the composition charged into the dispersion tank T3 in Example 8 is as follows.
Resin solution (L-2) 270 parts Fine particle (A-5) dispersion 45 parts Carbon dioxide 550 parts

Example 9
In Example 1, the fine particle (A-6) dispersion was used instead of the fine particle (A-1) dispersion, and the resin solution (L-2) was used instead of the resin solution (L-1). Except for the above, resin particles (C-9) were obtained in the same manner as in Example 1 in which the coatings derived from the fine particles (A) were formed on the surfaces of the resin particles (B). The weight ratio of the composition charged into the dispersion tank T3 in Example 9 is as follows.
Resin solution (L-2) 270 parts Fine particle (A-6) dispersion 45 parts Carbon dioxide 550 parts

Example 10
Into a beaker, normal decane and fine particle (A-1) dispersion liquid was added, and after mixing for 10 seconds at a rotation speed of 16000 rpm with a homomixer (manufactured by Primix), the resin solution (L-1) was added all at once with stirring. Dispersion was obtained for 1 minute to obtain a dispersion. Further, the dispersion was desolvated with an evaporator at 40 ° C. and 0.01 MPa, followed by filtration and drying to remove the solvent in the system, and the film derived from the fine particles (A) on the surface of the resin particles (B) Resin particles (C-10) were obtained. The weight ratio of the charged composition in Example 10 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-1) dispersion 45 parts Normal decane 120 parts

Example 11
Into a beaker, normal decane and fine particle (A-1) dispersion liquid was charged, mixed with a homomixer (Primics Co., Ltd.) at a rotation speed of 16000 rpm for 10 seconds, and then the resin solution (L-5) was charged all at once with stirring. Dispersion was obtained for 1 minute to obtain a dispersion. Further, the dispersion was desolvated with an evaporator at 40 ° C. and 0.01 MPa, followed by filtration and drying to remove the solvent in the system, and the film derived from the fine particles (A) on the surface of the resin particles (B) Resin particles (C-11) were obtained. The weight ratio of the charged composition in Example 11 is as follows.
Resin solution (L-5) 270 parts Fine particle (A-1) dispersion 45 parts Normal decane 120 parts

Example 12
Into a beaker, normal decane and fine particle (A-2) dispersion was charged, mixed with a homomixer (manufactured by Primics Co., Ltd.) at 16000 rpm for 10 seconds, and then the resin precursor (b0-1) and ion exchange were stirred. 20 parts of water was added all at once and dispersed for 1 minute to obtain a dispersion. Further, the dispersion was desolvated with an evaporator at 40 ° C. and 0.01 MPa, followed by filtration and drying to remove the solvent in the system, and the film derived from the fine particles (A) on the surface of the resin particles (B) Resin particles (C-12) were obtained. The weight ratio of the charged composition in Example 12 is as follows.
Resin precursor (b0-1) 270 parts Ion-exchanged water (water for elongation of ketimine) 20 parts Fine particle (A-2) dispersion 45 parts Normal decane 120 parts

Comparative Example 1
Comparative resin particles (C′-1) were obtained in the same manner as in Example 1 except that the fine particle (A-1) dispersion was not charged in Example 1. The weight ratio of the composition charged into the dispersion tank T3 in Comparative Example 1 is as follows.
Resin solution (L-1) 270 parts Carbon dioxide 550 parts

Comparative production example 1
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 100 parts of styrene, 138 parts of methyl methacrylate When 184 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and the vinyl resin (a′-1) (styrene-methyl methacrylate-butyl methacrylate-methacrylic acid EO adduct sulfate sodium salt was added. An aqueous dispersion of (polymer) was obtained. The volume average particle diameter of the aqueous dispersion measured with LA-920 was 0.15 μm. Further, the aqueous dispersion was freeze-dried to obtain comparative fine particles (A′-1).

Comparative Example 2
Comparative resin particles (C′-2) in the same manner as in Example 1, except that the comparative fine particles (A′-1) were previously charged in T3 instead of the fine particle (A-1) dispersion in Example 1. Got. The weight ratio of the composition charged into the dispersion tank T3 in Comparative Example 2 is as follows.
Resin solution (L-1) 270 parts Comparative fine particles (A′-1) 15 parts Carbon dioxide 550 parts

Comparative production example 2
In a reaction vessel equipped with a stirrer and a thermometer, water 683 parts, sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 139 parts of styrene, 138 parts of methyl methacrylate When 184 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and then the vinyl resin (a′-2) (styrene-methyl methacrylate-butyl acrylate-methacrylic acid EO adduct sulfate sodium salt was added. An aqueous dispersion (solid content concentration 20%) of comparative fine particles (A′-2) of (polymer) was obtained. The volume average particle diameter of the aqueous dispersion measured with LA-920 was 0.15 μm.

Comparative Example 3
In a beaker, 11 parts of an aqueous dispersion of comparative fine particles (A′-2), 80 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate, and 300 parts of ion-exchanged water were mixed and stirred to obtain a resin solution (L-1) 150. After mixing the parts, a TK homomixer (manufactured by Tokushu Kika) was used and mixed at a rotational speed of 12,000 rpm for 10 minutes. After mixing, the mixed solution was put into a reaction vessel equipped with a stirrer and a thermometer, and the solvent was removed at 50 ° C. for 2 hours, followed by filtration and drying to obtain resin particles (C′-3). . The weight ratio of the composition charged into the beaker in Comparative Example 3 is as follows.
Resin solution (L-1) 150 parts Aqueous dispersion of comparative fine particles (A′-2) 11 parts 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate 80 parts Ion-exchanged water 300 parts

Comparative production example 3
<Preparation of crystalline resin (a'-3)>
Into a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel, and nitrogen blowing tube, 500 parts of toluene was charged, and another glass beaker was charged with 350 parts of toluene and behenyl acrylate (directly containing 22 carbon atoms). Acrylic alcohol having a chain alkyl group: 150 parts of Blemer VA (manufactured by NOF)) and 10 parts of AIBN (azobisisobutyronitrile) are stirred and mixed at 20 ° C. to prepare a monomer solution. The dropping funnel was charged. After substituting nitrogen in the gas phase part of the reaction vessel, the monomer solution was added dropwise at 80 ° C. for 2 hours in a sealed state, and after aging at 85 ° C. for 2 hours after completion of the addition, toluene was added at 130 ° C. for 3 hours. Removal under reduced pressure gave a crystalline resin (a′-3). The crystallinity of this resin was 90%, the melting point was 65 ° C., and Mn was 8000.
<Preparation of fine particle (A'-3) dispersion>
After mixing 700 parts of normal hexane and 300 parts of resin (a′-3), the mixture is pulverized with zirconia beads having a particle diameter of 0.3 mm in a bead mill (Dynomill Multilab: manufactured by Shinmaru Enterprises), and milky white A comparative fine particle (A′-3) dispersion was obtained. The volume average particle diameter of this dispersion was 0.3 μm.

Comparative Example 4
In Example 1, a comparative fine particle (A′-3) dispersion was used instead of the fine particle (A-1) dispersion, and 228 parts of resin (b-1) instead of the resin solution (L-1) and (B-2) Except for the point where 57 parts were used and when the resin (b-1) was introduced into the dispersion tank T3 from the tank T1 and the pump P1, the temperature was raised to 100 ° C. and melted. Similarly, resin particles (C′-4) were obtained. The weight ratio of the composition charged into the dispersion tank T3 in Comparative Example 4 is as follows.
Resin (b-1) 228 parts Resin (b-2) 57 parts Comparative fine particle (A'-3) dispersion 45 parts Carbon dioxide 550 parts

Comparative production example 4
In a reaction vessel equipped with a stir bar and thermometer, 983 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 100 parts of styrene, 137 parts of methyl methacrylate , 184 parts of butyl acrylate, 1 part of (2-perfluorodecyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries), and 1 part of ammonium persulfate were stirred at 400 rpm for 15 minutes to obtain a white emulsion. It was. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and the vinyl resin (a′-4) (styrene-methyl methacrylate-butyl methacrylate-methacrylic acid EO adduct sulfate sodium salt An aqueous dispersion of (polymer) was obtained. The volume average particle diameter of the aqueous dispersion measured with LA-920 was 0.15 μm. Further, the aqueous dispersion was freeze-dried to obtain comparative fine particles (A′-4).

Comparative Example 5
In a beaker, 45 parts of an aqueous dispersion of comparative fine particles (A′-4), 80 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate, and 300 parts of ion-exchanged water were mixed and stirred to obtain a resin solution (L-1) 270. After mixing the parts, a TK homomixer (made by Tokushu Kika) was used and mixed for 10 minutes at a rotational speed of 12,000 rpm. After mixing, the mixture was poured into a reaction vessel equipped with a stirrer and a thermometer, and the solvent was removed at 50 ° C. for 2 hours, followed by filtration and drying to obtain resin particles (C′-5). The weight ratio of the composition charged into the beaker in Comparative Example 5 is as follows.
Resin solution (L-1) 270 parts Aqueous dispersion of comparative fine particles (A′-4) 45 parts 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate 80 parts Ion-exchanged water 300 parts

Evaluation results The resin particles obtained in Examples 1 to 12 and Comparative Examples 1 to 5 were evaluated for surface wettability, particle size distribution, heat-resistant storage stability, and moisture-resistant heat storage resistance by the evaluation methods described below, and the results are shown. 3.

<Surface wettability evaluation>
Add 0.1 g of resin particles into a 100 ml beaker, add 20 ml of ion-exchanged water, stir with a magnetic stirrer, float the resin particles on the liquid surface, drop acetone slowly, and the resin particles floating on the surface The acetone weight (Wa) and water weight (Ww) that disappeared were obtained with three significant digits, and the solubility parameter (δm) of the resin particle surface was calculated from the equation (1).
δm = (9.75 × Wa + 23.43 × Ww) / (Wa + Ww) (1)
<Evaluation of particle size distribution>
Resin particles were dispersed in an aqueous sodium dodecylbenzenesulfonate solution (concentration: 0.1%), and the volume average particle number / number average particle size of the resin particles (denoted as C in the table) was measured using a Coulter counter [Multisizer III (Beckman III Made by Coulter Co.)]. The smaller the volume average particle size / number average particle size, the sharper the particle size distribution.

<Evaluation of heat-resistant storage stability>
The heat resistant storage stability of the resin particles was evaluated by the following method. That is, the resin particles were allowed to stand for 24 hours in a dryer adjusted to 50 ° C., and evaluated according to the following criteria based on the degree of blocking.
○: Blocking does not occur.
Δ: Blocking occurs, but disperses easily when force is applied with a finger or the like.
X: Blocking occurs and does not disperse even when force is easily applied with a finger or the like.
<Evaluation of moisture and heat resistant storage stability>
The moisture resistance and heat resistant storage stability of the resin particles was evaluated by the following method. That is, the resin particles were allowed to stand for 24 hours in a thermo-hygrostat adjusted to 50 ° C. and 80% humidity, and evaluated according to the following criteria according to the degree of blocking.
○: Blocking does not occur.
Δ: Blocking occurs, but disperses easily when force is applied with a finger or the like.
X: Blocking occurs and does not disperse even when force is easily applied with a finger or the like.
<Evaluation of low-temperature meltability>
The melting temperature was evaluated by the following method.
Using a commercially available corona charging spray gun on a standard zinc phosphate-treated steel plate made by Nippon Test Panel, resin particles are electrostatically coated so that the film pressure is 20 to 40 μm, and the baking temperature is changed for evaluation. The minimum temperature at which the surface smoothness by visual confirmation after baking for 5 minutes was good was measured.

  The evaluation results and the physical property values of the resin particles of the present invention are shown in Tables 1 to 3.

  The resin particles obtained in Examples 1 to 12 have a small volume average particle size / number average particle size and a sharp particle size distribution, whereas the resin particles obtained in Comparative Examples 1, 2 and 4 are particles. Agglomerated and the particle size distribution deteriorated significantly. Moreover, although the resin particle obtained in Examples 1-12 was excellent in moisture-resistant heat-resistant storage stability, the resin particle obtained in Comparative Examples 3 and 5 was inferior in moisture-resistant heat-resistant storage stability. In addition, the resin particles obtained in Examples 1 to 12 (particularly Examples 1 to 9) also had an effect of being particularly excellent in low-temperature meltability (low melting temperature).

  The resin particles of the present invention are electrophotographic toners, paint additives, cosmetic additives, paper coating additives, slush molding resins, powder paints, electronic component manufacturing spacers, standard particles for electronic measuring instruments, It is useful as electronic paper particles, medical diagnostic carriers, electroviscous particles, and other molding resin particles.

T1: Resin solution tank T2: Fine particle dispersion tank T3: Dispersion tank (maximum operating pressure 20 MPa, maximum operating temperature 100 ° C., with stirrer)
T4: Particle recovery tank (maximum operating pressure 20 MPa, maximum operating temperature 100 ° C.)
F1: Ceramic filter (mesh: 0.5 μm)
T5: Solvent trap B1, B2: Carbon dioxide cylinder P1, P2: Solution pump P3, P4: Carbon dioxide pump V1: Valve V2: Pressure adjustment valve

Claims (8)

Fine particles (A) containing a crystalline resin (a) having the following (d1) and (d2) and / or (d3) as essential constituent units are formed on the surface of the resin particles (B) containing the resin (b). Resin particles (C), wherein the resin particles (C) are fixed, or a film containing the crystalline resin (a) is formed on the surface of the resin particles (B).
(D1) alkyl (meth) acrylate having 8 to 50 carbon atoms in the alkyl group (d2) perfluoroalkyl (alkyl) (meth) acrylate (d3) unsaturated dicarboxylic acid and / or anhydride thereof   The content of (d1) constituting the crystalline resin (a) is 30 to 90% by weight, and the content of (d2) and / or (d3) is 0.001 to 30% by weight. The resin particle of description.   The resin particles according to claim 1 or 2, wherein the crystalline resin (a) has a melting point of 40 to 110 ° C.   The resin particle according to any one of claims 1 to 3, which does not substantially contain a surfactant having a hydrophilic group.   The liquid or supercritical carbon dioxide (X) in which the fine particles (A) are dispersed is mixed with a solution (L) obtained by dissolving the resin (b) in the solvent (S). ) To form resin particles (C1) in which the fine particles (A) are fixed on the surface of the resin particles (B1) containing the resin (b) and the solvent (S), and then in a liquid or supercritical state. The method for producing resin particles according to any one of claims 1 to 4, comprising a step of obtaining resin particles (C) by removing carbon dioxide (X) and a solvent (S).   The liquid or supercritical carbon dioxide (X) in which the fine particles (A) are dispersed is mixed with the precursor (b0) of the resin (b), and (b0) is dispersed in (X). By reacting the body (b0), resin particles (C) in which the fine particles (A) are fixed to the surface of the resin particles (B) containing the resin (b) are formed, and then carbon dioxide in a liquid or supercritical state The method for producing resin particles according to any one of claims 1 to 4, comprising a step of obtaining resin particles (C) by removing (X).   The liquid or supercritical carbon dioxide (X) in which the fine particles (A) are dispersed and the solution (L0) in which the precursor (b0) of the resin (b) is dissolved in the solvent (S) are mixed, ( (L0) is dispersed in X), and the precursor (b0) is further reacted to fix the fine particles (A) on the surface of the resin particles (B1) containing the resin (b) and the solvent (S). The resin particles (C1) are formed, and then the liquid or supercritical carbon dioxide (X) and the solvent (S) are removed to obtain the resin particles (C). 5. The method for producing resin particles according to any one of 4 above.   A dispersion in which fine particles (A) are dispersed in a non-aqueous organic solvent (N), and a solution in which the resin (b) or the precursor (b0) of the resin (b) is dissolved in the organic solvent (S1) When the organic solvent (S1) solution of the precursor (b0) is used, the precursor (b0) is further reacted to contain the resin (b) in the fine particle (A) dispersion. By forming the resin particles (B) to be formed, a non-aqueous dispersion of the resin particles (C2) in which the fine particles (A) are fixed to the surface of the resin particles (B) is formed, and from the non-aqueous dispersion, The production of resin particles according to any one of claims 1 to 4, comprising a step of obtaining resin particles (C) by removing the organic solvent (S1) and the non-aqueous organic solvent (N). Method.

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