JP2007277511A - Method for producing resin particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide resin particles having a sharp particle size distribution and not having a hydrophilic component left in or on the surface of the resin particles; and to provide a method for producing the resin particles by using carbon dioxide in a supercritical state. <P>SOLUTION: The method for producing the resin particles comprises dispersing a molten liquid of a resin (b) or a solvent solution of the resin (b) in a dispersion medium (XO) obtained by dispersing fine particles (A) in carbon dioxide (X) in a liquid or super critical state, and containing a dispersion stabilizer (D) having at least one group of a dimethylsiloxane group and a fluorine-containing functional group to afford a dispersion (XI) of the fine particles (C1), and removing the carbon dioxide (X) in the liquid or supercritical state by reducing the pressure to afford the resin particles (C) wherein the fine particles (A) is attached to the surfaces of the resin particles (B) comprising the resin (b). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to resin particles having a uniform particle size, and a method for producing the same, and more particularly to a method for producing the resin particles using carbon dioxide in a supercritical state.

Conventionally, a resin solution in which a resin is previously dissolved in a solvent is dispersed in an aqueous medium in the presence of a dispersing (auxiliary) agent such as inorganic particles, a surfactant, a water-soluble polymer, etc. A method (dissolution suspension method) for removing resin and obtaining resin particles is known (for example, see Patent Document 1).
According to this method, the particle size is fine and the particle size distribution not only in addition polymerization resins in which relatively monodisperse particles are easily obtained by dispersion polymerization, seed polymerization method, etc., but also in polycondensation resins and polyaddition resins It is possible to obtain sharp particles.
However, this method uses a surfactant having a hydrophilic group (surfactant, polymer protective colloid, surfactant fine particles) for the purpose of reducing the free energy of the interface in water during production or imparting dispersion stability in water. Etc.) must be used. When the surface active substance remains in the resin particle or on the surface, it contains water-soluble impurities such as a surfactant having a hydrophilic group, so that the powder characteristics, electrical characteristics, thermal characteristics, chemical properties of the resin particles There was a drawback that performance such as stability was impaired. On the other hand, as a particle forming method in a non-aqueous medium, a method of spraying a resin solution into a supercritical fluid (for example, see Patent Documents 2 and 3) is known.
JP-A-9-319144 WO97 / 31691 pamphlet WO95 / 01221 pamphlet

According to the method of spraying the resin solution in the supercritical fluid, particles having excellent powder characteristics, electrical characteristics, etc. are not required because a hydrophilic component is not required and the surface active substance does not remain in the resin particles or on the surface. Although it can be obtained, there is a problem that it is difficult to obtain a sharp particle size distribution.
An object of the present invention is to obtain resin particles in which no hydrophilic component remains in or on the resin particles and the particle size distribution is sharp.

The present invention has been made in view of the above circumstances in the prior art. That is, the present invention
Resin (b) or solvent solution of resin (b), or precursor (b0) of resin (b) or solvent solution thereof is dispersed in carbon dioxide (X) in a liquid or supercritical state, and the pressure is reduced. In the method for producing resin particles by removing carbon dioxide (X) in a liquid or supercritical state, a dispersion stabilizer (D) having at least one of a dimethylsiloxane group and a functional group containing fluorine (D ) And fine particles (A) are used together to obtain resin particles (C) in which the fine particles (A) are adhered to the surfaces of the resin particles (B) made of the resin (b). It is.
Further, in the present invention, preferably, the fine particles (A) are liquid or supercritical carbon dioxide (D) containing a dispersion stabilizer (D) having at least one of a dimethylsiloxane group and a functional group containing fluorine. A dispersion (X1) of resin particles (C1) obtained by dispersing a melt of resin (b) or a solvent solution of resin (b) in a dispersion medium (X0) dispersed in X) By removing the liquid or supercritical carbon dioxide (X) from the dispersion (X1) by reducing the pressure, the fine particles (A) are formed on the surface of the resin particles (B) made of the resin (b). A method for producing resin particles, characterized in that the resin particles (C) to be adhered are obtained (hereinafter referred to as a preferred first invention);
Dispersion formed by dispersing fine particles (A) in liquid or supercritical carbon dioxide (X) containing a dispersion stabilizer (D) having at least one of a dimethylsiloxane group and a functional group containing fluorine. In the dispersion (X2) of the resin particles (C2) obtained by dispersing the precursor (b0) of the resin (b) or the solvent solution thereof in the medium (X0), the precursor (b0) is subjected to a polymerization reaction. Thereafter, the surface of the resin particles (B) in which the fine particles (A) are made of the resin (b) by removing the liquid or supercritical carbon dioxide (X) from the dispersion (X2) by reducing the pressure. A resin particle production method characterized in that the resin particle (C) adhered to the resin particle (C) is obtained (hereinafter referred to as a preferred second invention);
The resin (b) melt or the resin (b) solvent solution containing the dispersion stabilizer (D) having at least one of a dimethylsiloxane group and a fluorine-containing functional group, the fine particles (A) are liquid Alternatively, by dispersing the dispersion (X3) of resin particles (C3) obtained by dispersing in a dispersion medium (X02) dispersed in carbon dioxide (X) in a supercritical state, the pressure is reduced. Resin particles (C) in which fine particles (A) are adhered to the surface of resin particles (B) made of resin (b) by removing carbon dioxide (X) in a liquid or supercritical state from dispersion (X3) A method for producing resin particles (hereinafter referred to as a preferred third invention);
Resin (b) precursor (b0) or solvent solution thereof containing a dispersion stabilizer (D) having at least one of a dimethylsiloxane group and a fluorine-containing functional group, the fine particles (A) are liquid or Polymerization reaction of precursor (b0) in dispersion (X4) of resin particles (C4) obtained by dispersion in dispersion medium (X02) dispersed in carbon dioxide (X) in a supercritical state After that, by removing the carbon dioxide (X) in a liquid or supercritical state from the dispersion (X4) by reducing the pressure, the fine particles (A) of the resin particles (B) made of the resin (b) A resin particle manufacturing method (hereinafter referred to as a preferred fourth invention) characterized in that the resin particle (C) adhered to the surface is obtained.

  The resin particles obtained by the production method of the present invention are resin particles which do not contain a surfactant having a hydrophilic group (surfactant, polymer protective colloid, surfactant fine particles, etc.) and have a sharp particle size distribution. . Therefore, resin particles having high hydrophobicity and excellent electrical characteristics and powder characteristics can be obtained.

The present invention is described in detail below.
In the present invention, resin (b) or a solvent solution of resin (b), or a precursor (b0) of resin (b) or a solvent solution thereof is dispersed in carbon dioxide (X) in a liquid or supercritical state, Dispersion having at least one of a dimethylsiloxane group and a fluorine-containing functional group in a method for producing resin particles by removing liquid or supercritical carbon dioxide (X) by reducing the pressure. Resin characterized in that the stabilizer (D) and the fine particles (A) are used in combination to obtain resin particles (C) in which the fine particles (A) are adhered to the surface of the resin particles (B) made of the resin (b). Although it is a manufacturing method of particle | grains, it is specifically the preferable 1st-4th invention described below.
First, the manufacturing method of the resin particle (C) which is preferable 1st invention is demonstrated.
In a preferred first aspect of the invention, a melt of the resin (b) or a solvent solution of the resin (b) is used as a dispersion stabilizer having at least one group of fine particles (A), dimethylsiloxane groups and fluorine-containing functional groups ( By reducing the pressure of the dispersion (X1) of the resin particles (C1) obtained by dispersing in the dispersion medium (X0) comprising carbon dioxide (X) in a liquid or supercritical state containing D) Resin particles (C) are obtained by removing (X) from dispersion (X1). While the fine particles (A) are adsorbed on the surface, the dispersed resin (b) is grown to form resin particles (C1). In the process of particle growth, until the fine particles (A) completely cover the surface, the dispersed resin (b) agglomerates and continues particle growth, so the particle size of the grown particles is averaged and a sharp particle size distribution is obtained. Resin particles are obtained.
In the present invention, the fine particles (A) are not particularly limited as long as they are inorganic or organic particulate substances, and may be used alone or in combination of two or more depending on the purpose. That is, any of inorganic fine particles (A1), organic fine particles (A2), and combinations of (A1) and (A2) may be used.

  Examples of the inorganic fine particles (A1) include silica, diatomaceous earth, alumina, zinc oxide, titania, zirconia, calcium oxide, magnesium oxide, iron oxide, copper oxide, tin oxide, chromium oxide, antimony oxide, yttrium oxide, cerium oxide, Metal oxides such as samarium oxide, lanthanum oxide, tantalum oxide, terbium oxide, europium oxide, neodymium oxide, ferrites, metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, heavy Calcium carbonate, light calcium carbonate, metal carbonate such as zinc carbonate, barium carbonate, dosonite, hydrotalcite, metal sulfate such as calcium sulfate, barium sulfate, gypsum fiber, calcium silicate (wollastonite, zonotlite), kaolin, clay Metal silicates such as talc, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, glass flakes, metal nitrides such as aluminum nitride, boron nitride, silicon nitride, potassium titanate, Metal titanates such as calcium titanate, magnesium titanate, barium titanate, lead zirconate titanate aluminum borate, metal borates such as zinc borate and aluminum borate, metal phosphates such as tricalcium phosphate Metal sulfides such as molybdenum sulfide, metal carbides such as silicon carbide, carbons such as carbon black, graphite, and carbon fiber, gold, silver, and other inorganic particles.

  Examples of the organic fine particles (A2) include vinyl resins, urethane resins, epoxy resins, ester resins, polyamides, polyimides, silicone resins, fluororesins, phenol resins, melamine resins, benzoguanamine resins, urea resins, aniline resins, and ionomer resins. , Known organic resin fine particles (A21) such as polycarbonate, cellulose and a mixture thereof. Also, ester wax (carnauba wax, montan wax, rice wax, etc.), polyolefin wax (polyethylene, polypropylene, etc.), paraffin wax, ketone wax, ether wax, long chain fatty alcohol, long chain fatty acid and these Examples thereof include organic wax fine particles (A22) such as a mixture, and metal salt fine particles (A23) of a long chain fatty acid. In addition, various organic dyes or organic pigments such as azo, phthalocyanine, condensed polycyclic, dye lake and the like, which are generally used as colorants, and derivatives thereof can be used.

The fine particles (A) may be used as they are, and in order to have the adsorptivity to the resin particles (B), for example, surface treatment with a coupling agent such as silane, titanate or aluminate, various surfactants. The surface may be modified by surface treatment with, coating treatment with wax or polymer, or the like.
Fine particles (A) include metal oxide, metal hydroxide, metal carbonate, metal sulfate, metal silicate, metal nitride, metal phosphate, metal borate, metal titanate, metal sulfide, At least one selected from the group consisting of at least one inorganic fine particle (A1) selected from the group consisting of carbons, urethane resin, epoxy resin, vinyl resin, polyester resin, melamine resin, benzoguanamine resin, fluororesin, and silicone resin. It is preferable to use a kind of organic resin fine particles (A21), long chain fatty acid metal salt fine particles (A23), or a mixture of at least two selected from the group consisting of (A1), (A21) and (A23). .

  The resin particles (B) are composed of the resin (b). In the present invention, the resin (b) can be any resin, and may be a thermoplastic resin or a thermosetting resin. For example, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester Examples thereof include resins, polyamide resins, polyimide resins, silicon resins, fluorine resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin (b), two or more of the above resins may be used in combination. Among these, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, and a combination thereof are preferable from the viewpoint that a dispersion of fine spherical resin particles is easily obtained.

  The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. Examples of the vinyl monomer 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-other than the above Olefin and the like; 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 and salts thereof: C3-C30 unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and their anhydrides and monoalkyl (C1-C24) esters such as (meth) Acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester Carboxyl group-containing vinyl monomers such as cinnamic acid.

(3) Sulfonic 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 sulfone Acids; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methylstyrene sulfonic acid; sulfo (hydroxy) alkyl- (meth) acrylates or (meth) acrylamides such as sulfopropyl (meth) acrylates, 2-hydroxy -3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2- Hydroxypropane sulfonic acid, 2- (meth) 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 sulfate or Sulfonic acid group-containing monomers; and salts thereof.

(4) Phosphoric acid group-containing vinyl monomers and salts thereof: (meth) acryloyloxyalkyl (C1-C24) phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (Meth) acryloyloxyalkyl (C1-24) phosphonic acids, for example 2-acryloyloxyethylphosphonic acid. Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary grades. An ammonium salt is mentioned.

(5) Hydroxyl group-containing vinyl monomers: hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, black Tyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(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-vinyl Pyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, (6-2) Amido group-containing vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butylacrylamide, 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, cyanoacrylate, etc. (6-4) Quaternary ammonium cation group-containing vinyl monomers: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylamino D Quaternization of tertiary amine group-containing vinyl monomers such as til (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine and the like (4 using a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate, etc.) Classified)
(6-5) Nitro group-containing vinyl monomers: nitrostyrene and the like.

(7) Epoxy group-containing vinyl monomers: glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like.

(8) Halogen element-containing vinyl monomers: vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, and the like.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones: (9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate , Vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are linear, branched chain having 2 to 8 carbon atoms) Or an alicyclic group), a dialkyl maleate (two alkyl groups are linear, 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 ( Molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 50 ) Monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate, 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.], 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, (9-3) vinyl ketones such as vinyl Methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone; vinyl sulfone such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyls Lufon, divinyl sulfoxide, etc.

(10) Other vinyl monomers: isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like. Examples of the copolymer of vinyl monomers include polymers obtained by copolymerizing any of the above monomers (1) to (10) with a binary or higher number in an arbitrary ratio. (Meth) acrylic acid ester copolymer, styrene-butadiene copolymer, (meth) acrylic acid-acrylic acid ester copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meta ) Acrylic acid copolymer, styrene- (meth) acrylic acid, divinylbenzene copolymer, styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer, and the like.

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

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) S), etc .; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above bisphenol; other, polylactone Examples thereof include diols (such as poly ε-caprolactone diol) and polybutadiene diols. 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 novolak resins. Acrylic polyols [Copolymers of hydroxyethyl (meth) acrylate and other vinyl monomers]
Of these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and alkylene oxide adducts of novolac resins, and particularly preferred are alkylene oxide adducts of novolac resins.

  Dicarboxylic acid (13) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, dodecenyl succinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, etc.); alkenylene dicarboxylic acid (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 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 polyisocyanates, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, Oxazolidone group-containing modified products) and mixtures of two or more thereof. Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, and 2,4 ′. -And / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with an aromatic amine (aniline) or mixtures thereof; diaminodiphenylmethane and a small amount (eg 5 to 20 wt.] %) Of trifunctional or higher polyamines] phosgenates: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4. -Trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6- Aliphatic polyisocyanates such as diisocyanatohexanoate, etc. Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmedium. 4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2 , 5- and / or 2,6-norbornane diisocyanate, etc. Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), etc. The modified polyisocyanates include urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanates. Nurate group, oxazoly Such as down-containing modified products thereof. Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified polyisocyanates such as urethane-modified TDI, and mixtures of two or more of these [for example, modified MDI and urethane-modified TDI (Combined use with an isocyanate-containing prepolymer)] is included. Of these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

  Examples of polyamine (16) include aliphatic polyamines (C2 to C18): (1) aliphatic polyamine {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) , Polyalkylene (C2 to C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; (2) these alkyls (C1 to C4) ) Or substituted hydroxyalkyl (C2 to C4) [dialkyl (C1 to C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine Methyliminobispropylamine etc.]; (3) Alicyclic or heterocyclic aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (4) Aromatic ring-containing aliphatic amines (C8 -C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamines (C4 -C15): 1,3-diaminocyclohexane, Heterocyclic polyamines (C4 to C15) such as isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline): piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine Aromatic polyamines (C6 -C20) such as 1,4 bis (2-amino-2-methylpropyl) piperazine: 5) Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), Diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ', 4 "-triamine, naphthylenediamine, etc. Aromatic polyamines having nuclear substituted alkyl groups (C1-C4 alkyl groups such as methyl, ethyl, n- and i-propyl, butyl, etc.), such as 2,4- and 2,6-tolylenediamine, crude tolylenediamine , Diethyltolylenediamine, 4,4′-diamino-3,3 ′ -Dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1 , 3-Dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene 2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2 , 4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2 6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6-dibutyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine 3,3 ′, 5,5′-tetraisopropylbenzidine, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4, 4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetrabutyl-4,4'-diaminodiphenylmethane, 3,5 -Diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,5-diisopropyl-3'-methyl-2', 4-diaminodiphenylmethane, 3,3'-diethyl -2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5 , 5′-tetraisopropyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5′-tetraisopropyl-4, 4'-diaminodiphenylsulfone, etc.), and mixtures of these isomers in various proportions; (6) nuclear substituted electron withdrawing groups (halogens such as Cl, Br, I, F; alkoxy groups such as methoxy, ethoxy; nitro; Group, etc.) [methylene bis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine] 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4 -Aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,5'-dibromo-diphenylmethane, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, bis (4-amino-3 -Chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide Bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxy) Enyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4'-methylenebis (2-bromoaniline), 4,4'-methylenebis (2-fluoroaniline), 4-aminophenyl-2- Chloroaniline etc.]; (7) Aromatic polyamine having a secondary amino group [partial or partial -NH2 of the aromatic polyamine of the above (4) to (6) is -NH-R '(R' is an alkyl group) For example, lower alkyl groups such as methyl and ethyl)] [4,4'-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.], polyamide polyamine: dicarboxylic An acid (such as a dimer acid) and an excess (more than 2 moles per mole of acid) of a polyamine (such as the above-mentioned alkylene diamine, polyalkylene polyamine); And low molecular weight polyamide polyamines obtained by condensation of polyether polyamines: hydrides of cyanoethylated polyether polyols (polyalkylene glycols and the like).

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

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

  The polyepoxide (18) of the present invention is not particularly limited as long as it has two or more epoxy groups in the molecule. What has preferable 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material as a preferable polyepoxide (18). The epoxy equivalent of the polyepoxide (18) (molecular weight per epoxy group) is usually 65 to 1000, preferably 90 to 500. When the epoxy equivalent exceeds 1000, the cross-linked structure becomes loose and the physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are deteriorated. On the other hand, it is difficult to synthesize an epoxy equivalent of less than 65. is there.

  Examples of the polyepoxide (18) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols. Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyldi Glycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, Of glycol ether of enolic or cresol novolac resin, glycidyl ether of limonene phenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained by condensation reactions, polyglycidyl ethers of polyphenols obtained by condensation reactions of resorcin and acetone, and the like. 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. Furthermore, in the present invention, the aromatic system is obtained by reacting a polyol with the above-mentioned two reactants, such as triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol. The glycidyl group-containing polyurethane (pre) polymer and an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A are also included. Heterocyclic polyepoxy compounds include trisglycidyl melamine; alicyclic polyepoxy compounds include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl). Ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexyl) Methyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester, and the like. The alicyclic group also includes a hydrogenated product of the aromatic polyepoxide compound; examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyvalent aliphatic alcohols and polyglycidyl esters of polyvalent fatty acids. Body, and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether Can be mentioned. Examples of 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 type also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more of the polyepoxides of the present invention may be used in combination.

  The number average molecular weight (measured by GPC, hereinafter abbreviated as Mn) of the resin (b) is 2-5 million, preferably 2,000-500,000, and the SP value is 7-18, preferably 8-14. The Mn of the resin (b) may be appropriately adjusted within a preferable range depending on the use. For example, when used for a powder coating, 2,000 to 500,000, preferably 4,000 to 200,000, when used for an electrophotographic toner, 1,000 to 5,000,000, preferably 2,000 to 500,000. Moreover, when it is desired to improve the heat resistance, water resistance, chemical resistance, uniformity of particle diameter, etc. of the resin particles (C), a crosslinked structure may be introduced into the resin (b). Such a cross-linked structure may be any cross-linked form such as covalent bond, coordinate bond, ionic bond, hydrogen bond, and the like. In the case of introducing a crosslinked structure into the resin (b), the molecular weight between crosslinking points is 30 or more, preferably 50 or more.

The glass transition temperature (Tg) of the resin (b) is 0 ° C to 300 ° C, preferably 20 ° C to 250 ° C. If it is below this range, problems such as deterioration in storage stability of the particles occur. In addition, Tg in this invention is a value calculated | required from DSC measurement.
The Tg of the resin (b) is preferably appropriately adjusted depending on the application. For example, when used for a powder coating, it is 0 ° C. to 200 ° C., preferably 35 ° C. to 150 ° C., and when used for an electrophotographic toner, 20 It is 80 degreeC-300 degreeC, Preferably it is 80 degreeC-250 degreeC.

  The resin particles (C) are particles obtained by attaching the fine particles (A) to the surfaces of the resin particles (B). The particle size of the fine particles (A) is smaller than the particle size of the resin particles (B). The value of the particle size ratio [volume average particle size of fine particles (A)] / [volume average particle size of resin particles (C)] is 0.001 to 0.1, preferably 0.002 to 0.08, more preferably Is 0.003 to 0.06, particularly preferably 0.01 to 0.05. Within the above range, (A) is efficiently adsorbed on the surface of (B), so that the particle size distribution of (C) obtained becomes narrow.

  The volume average particle diameter of the fine particles (A) can be appropriately adjusted within the above range of the particle diameter ratio so as to be a particle diameter suitable for obtaining the resin particles (C) having a desired particle diameter. For example, when it is desired to obtain resin particles (C) having a volume average particle diameter of 1 μm, the range is preferably 0.0005 to 0.3 μm, particularly preferably in the range of 0.001 to 0.2 μm, and 10 μm resin particles (C). In the case of obtaining particles (C) of preferably 0.005 to 3 μm, particularly preferably 0.05 to 2 μm and 100 μm, preferably 0.05 to 30 μm, particularly preferably 0. 1-20 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, Ltd.), a laser particle size distribution measuring device (for example, LA-920: manufactured by HORIBA, Ltd.), Multitizer III (Beckman).・ Measured by Coulter, Inc.

The solubility parameter in the evaluation of the surface wettability of the resin particles (C) (using an acetone / water mixed solution) is 9.8 to 21, preferably 9.8 to 20. If it exceeds 21, the particle surface becomes hydrophilic and the electrical properties deteriorate. This measurement method cannot measure less than 9.8.
The surface wettability evaluation method is as follows. That is, 0.1 g of resin particles (C) is put in a 100 ml beaker, 20 ml is added thereto, stirred with a magnetic stirrer, fine particles (C) are floated on the liquid surface, and acetone is dripped little by little to float on the surface. The acetone mass (Wa) and water mass (Ww) at which (C) is eliminated are obtained, and the solubility parameter (δm) on the surface (C) is calculated from the equation (1). (Surface wettability evaluation is based on Journal of Color Material Association, No. 73 [3], 2000, P132-138.)
δm = (9.75 × Wa + 23.43 × Ww) / (Wa + Ww) (1)

The volume average particle diameter of the resin particles (C) is 0.01 to 300 μm, preferably 0.1 to 100 μm, and more preferably 0.5 to 50 μm. When it is less than 0.01 μm, the handling property as a powder is deteriorated. When it exceeds 300 μm, the particle size distribution is deteriorated.
The ratio DVc / DNc between the volume average particle diameter DVc of (C) and the number average particle diameter DNc of (C) is 1.0 to 1.5, preferably 1.0 to 1.4, more preferably 1.0. ~ 1.3. If it exceeds 1.5, the powder properties (fluidity, charging uniformity, etc.) are significantly deteriorated.

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

  From the viewpoints of particle size uniformity, storage stability and the like of the resin particles (C), the resin particles (C) are usually 0.01 to 50% by weight of (A) and 50 to 99.99% by weight of (B). Preferably, it consists of 0.1 to 40% by weight of (A) and 60 to 99.9% by weight of (B). (A) in (C) can be measured by a known method. For example, when inorganic fine particles such as silica and titania are used as (A), it can be measured by fluorescent X-rays.

The dispersion stabilizer (D) 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.
More specifically, the monomer (or reactive oligomer) (M1-1) having a dimethylsiloxane group described later and / or a monomer (M1-2) containing fluorine and the resin (b) described above are configured. A copolymer with the monomer (M2) is preferred. The form of copolymerization may be random, block or graft, but block or graft is preferred.

For example, when the resin (b) is a vinyl resin, the monomer (or reactive oligomer) (M1-1) having a dimethylsiloxane group is preferably methacryl-modified silicone and has a structure represented by the following formula.
(CH ₃ ) ₃ SiO ((CH ₃ ) ₂ SiO) _a Si (CH ₃ ) ₂ R (where a is an average value of 15 to 45, and R is an organically modified group containing a methacryl group). Examples of are 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. As the monomer (M2) constituting the resin (b), it is preferable to use the above-described vinyl monomers (1) to (10).

  When the resin (b) is a urethane resin, (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 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. (M2) includes the above-described polyisocyanate (15), water, diol (11), trivalent or higher polyol (12) dicarboxylic acid (13), trivalent or higher polycarboxylic acid (14), polyamine (16). Polythiol (17) and the like are preferable.

When the resin (b) has an acid value, the dispersion stabilizer (D) 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.
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 range of the weight average molecular weight of the dispersion stabilizer (D) is preferably 100 to 100,000, more preferably 200 to 50,000, and particularly preferably 500 to 30,000. Within this range, the dispersion stabilizing effect of (D) is improved.
The dispersion stabilizer (D) in the preferred first invention is preferably dissolved in carbon dioxide (X) under temperature and pressure conditions for dispersing the molten solution of the resin (b) or the solvent solution of the resin (b).
The amount of the dispersion stabilizer (D) added is preferably from 0.01 to 50% by weight, more preferably from 0.02 to 40% by weight, particularly preferably from the viewpoint of dispersion stability, based on the weight of the resin (b). 0.03 to 30% by weight.

  In the present invention, any method may be used to disperse the fine particles (A) in the liquid or supercritical carbon dioxide (X). For example, (A) and (X) are charged in a container, and stirring or ultrasonic waves are introduced. Examples thereof include a method of directly dispersing (A) in (X) by irradiation, a method of introducing the solvent dispersion of (A) into (X), and the like. In this way, a dispersion medium (X0) in which (A) is dispersed in (X) is obtained. The fine particles (A) are preferably those that do not dissolve in (X) and are stably dispersed in (X).

The melt of the resin (b) can be obtained by heating within a range where the resin (b) does not deteriorate. When the viscosity is not sufficiently lowered by heating, it may be dissolved in the solvent (U).
In general, the resin (b) is not easily lowered to a viscosity at which the particles can be sufficiently finely dispersed by heating alone, and the heat (denaturation) is often caused to the resin (b) by heating. The resin (b) having a lower viscosity is more likely to have a sharper particle size distribution, and therefore it is preferable to use a solvent (U).
The concentration of the solvent solution of the resin (b) is preferably 10 to 90%, more preferably 20 to 80%.

  Examples of the solvent (U) used in the present invention include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, and cyclohexane. Solvents: Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, etc. Ester solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, Ketone solvents such as til isobutyl ketone, di-n-butyl ketone and cyclohexanone; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol An amide solvent such as dimethylformamide and dimethylacetamide; a sulfoxide solvent such as dimethyl sulfoxide; a heterocyclic compound solvent such as N-methylpyrrolidone; and a mixed solvent of two or more of these.

The melt of the resin (b) or the solvent solution of the resin (b) is preferably moderate viscosity because it is dispersed in (X), and is preferably 100 Pa · s or less, more preferably from the viewpoint of particle size distribution. 10 Pa · s or less. 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) (the calculation method of the SP value is according to Document 1 below) is usually 8 to 16, preferably 9 to 14.
Literature 1: Polymer Engineering and Science, February, 1974, Vol. 14, no. 2 P.I. 147-154

  In the resin (b) of the present invention, other additives (pigments, fillers, antistatic agents, colorants, release agents, charge control agents, ultraviolet absorbers, antioxidants, antiblocking agents, heat stabilizers, Flame retardant etc. may be mixed. As a method for adding other additives in the resin (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, any method may be used as a method of dispersing the melt of the resin (b) or the solvent solution of the resin (b) in (X0).
As a specific example, a method of dispersing the solvent solution of the resin (b) with a stirrer or a disperser, the solvent solution of the resin (b) is sprayed into the (X0) via a spray nozzle to form droplets, A method in which a resin in a droplet is supersaturated to precipitate resin particles (known as ASES: Aerosol Extraction System), a resin solution from a coaxial multiple tube (double tube, triple tube, etc.), (X1 ) And other high pressure gases, entrainers, etc., are simultaneously ejected from separate tubes to promote particle breakup by applying external stress to the droplets (known as SEDS: Solution Enhanced Dispersion by Supercritical Fluids) ) And a method of irradiating ultrasonic waves.

In this way, the resin (b) is dispersed in (X0), and the dispersed resin (b) is grown while adsorbing the fine particles (A) on the surface. Resin particles (C1) formed by adhering the fine particles (A) 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 a solvent solution of the resin (b) is used, it is not preferable that the solvent phase is separated in addition to the liquid in which (C1) is dispersed or the phase containing supercritical carbon dioxide. Therefore, when the solvent solution of the resin (b) is dispersed in (X0), it is preferable to set the amount of the solvent solution of (b) with respect to (X0) so that the solvent phase is not separated.

  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 (the pressure of the present invention indicates the total pressure in the case of a mixed gas of two or more components).

  In the production method of the present invention, the operation performed in carbon dioxide (X) in a liquid or supercritical state is preferably performed at the following temperature. In order to prevent carbon dioxide from undergoing a phase transition in the pipe during decompression and block the flow path, the temperature is preferably 30 ° C. or higher, and the fine particles (A), resin particles (B), and resin particles (C) In order to prevent thermal deterioration, 200 ° C. or lower is preferable. 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 temperatures of (X0) and (X1).

In the production method of the present invention, the operation performed in carbon dioxide (X) in a liquid or supercritical state is preferably performed at the following pressure. In order to satisfactorily disperse (C) 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 media (X0) and (X1).
In the production method of the present invention, the temperature and pressure of the operation carried out in liquid or supercritical carbon dioxide (X) are such that resin (b) is not dissolved in (X) and (b) is agglomerated and combined. It is preferable to set within a possible 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 (X0) and (X1).

The mass fraction of carbon dioxide in (X) in the present invention is usually 70% or more, preferably 80% or more, and more preferably 90% or more.
In order to adjust the physical property values (viscosity, diffusion coefficient, dielectric constant, solubility, interfacial tension, etc.) as the dispersion medium, other substances (e) may be appropriately contained in (X), for example, nitrogen, helium, argon And an inert gas such as air.

  When the dispersion (X1) in which the resin particles (C1) are dispersed is depressurized to obtain resin particles (C), the pressure may be reduced stepwise by providing multiple pressure-controlled containers. The pressure may be reduced to normal temperature and normal pressure at once. The collection method of the resin particles (C) 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 (C) may be collected after depressurization, or may be collected under high pressure before depressurization and then depressurized. As a method of taking out the resin particles (C) from under high pressure when the pressure is reduced after being collected under high pressure, the collection container may be depressurized by batch operation, or continuously with a rotary valve. An operation may be performed.

When the dispersion (X1) contains the solvent (U), if the container is decompressed as it is, the solvent dissolved in (X1) will condense and the resin particles (C) may be re-dissolved, or the resin particles ( When collecting C), there may be a problem that the resin particles (C) are united with each other.
Accordingly, the dispersion (X1) or dispersion (X3) obtained by dispersing the solvent solution of the resin (b) is further mixed with liquid or supercritical carbon dioxide (X) to obtain resin particles (C1). Alternatively, it is preferable to extract the solvent from the resin particles (C3) into a carbon dioxide phase, that is, to further reduce the pressure after substituting the carbon dioxide containing the solvent with (X).

In the mixing method of (X1) and (X), (X) at a pressure higher than (X1) may be added, and (X1) may be added into (X) at a lower pressure than (X1). From the viewpoint of ease of continuous operation, the latter is more preferable.
The amount of (X) mixed with (X1) is preferably 1 to 50 times the volume of (X1), more preferably 1 to 40 times, and most preferably from the viewpoint of preventing coalescence of the resin particles (C). 1 to 30 times. By removing or reducing the solvent contained in the resin particles (C1) as described above, it is possible to prevent the resin particles (C1) from uniting with each other.
As a method of further substituting the carbon dioxide containing the solvent with (X), after the resin particles (C) are once supplemented with a filter or cyclone, the pressure is maintained and (X) is circulated until the solvent is completely removed. The method of letting it be mentioned.
The amount of (X) to be circulated is preferably 1 to 100 times, more preferably 1 to 50 times, and most preferably 1 to 30 times the volume of (X1) from the viewpoint of solvent removal from (X1). It is.

Even when the dispersion (X3) contains the solvent (U), it is preferably carried out in the same manner as in the case of the dispersion (X1).
Further, when the dispersion (X2) or (X4) contains the solvent (U), the precursor (b0) of the resin (b) is subjected to the polymerization reaction and then the same as in the case of the dispersion (X1). Is preferred.

Next, the manufacturing method of the resin particle (C) which is preferable 2nd invention is demonstrated.
In a preferred second invention, the dispersion stabilizer having the precursor (b0) of the resin (b) or a solvent solution thereof having the fine particles (A) and at least one group of a functional group containing a dimethylsiloxane group and fluorine. In a dispersion (X2) of fine particles (C2) obtained by dispersing in a dispersion (X0) composed of carbon dioxide (X) in a liquid or supercritical state containing (D), (b0) is subjected to polymerization reaction The resin particles (C) are obtained by removing the medium (X) from the dispersion medium (X2) by reducing the pressure.
In a preferred second invention, instead of the melt of the resin (b) or the solvent solution of the resin (b) of the preferred first invention, a precursor (b0) of the resin (b) or a solvent solution thereof is used, Except for the point that (b0) is polymerized in dispersion (X2), the same operation as that of the preferred first invention can be used. The same dispersion stabilizer (D) as that of the preferred first invention can be used. In the present invention, since the particle size distribution of the resin particles (C) tends to be sharper when the dispersed phase component has a lower viscosity, the precursor (b0) of the (b) is more used than the resin (b). preferable.

  In the present invention, the precursor (b0) of the resin (b) is not particularly limited as long as it can become the resin (b) by a chemical reaction. For example, when the resin (b) is a vinyl resin , (B0) includes the above-mentioned vinyl monomers (which may be used alone or mixed) and solvent solutions thereof, and the resin (b) is a condensation resin (for example, polyurethane resin, epoxy) In the case of (resin, polyester resin), (b0) is exemplified by a combination of a prepolymer (α) having a reactive group and a curing agent (β).

  When a vinyl monomer is used as the precursor (b0), (b0) may contain an 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, isobutyryl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxy Dicarbonate, 2,4-dichlorobenzoyl peroxide, t-butylperoxybivalate, 3,5,5-trimethylhexanonyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, Propionitrile peroxide, succinic acid peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, parachlorobenzoy Peroxide, t-butyl peroxyisobutyrate, t-butyl peroxymaleic acid, t-butyl peroxylaurate, cyclohexanone peroxide, t-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5 -Dibenzoylperoxyhexane, t-butylperoxyacetate, t-butylperoxybenzoate, diisobutyldiperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-dit-butyl Peroxyhexane, t-butyl cumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, pinane hydroperoxide Kisaido, 2,5-dimethyl-2,5-dihydro peroxide, cumene peroxide and the like (I-2) water-soluble peroxide polymerization initiators: hydrogen peroxide, peracetic acid, ammonium persulfate, and the like sodium persulfate.

(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: azobis Amidinopropane 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, mercaptans In combination with oil-soluble reducing agents such as organometallic compounds (triethylaluminum, triethylboron, diethylzinc, etc.) (III-2) Water-based redox polymerization initiators: water-soluble such as persulfate, hydrogen peroxide, hydroperoxide Examples thereof include a combination of a peroxide and a water-soluble inorganic or organic reducing agent (divalent iron salt, sodium hydrogen sulfite, alcohol, polyamine, etc.).

   When the initiator is used, it is preferable to mix with (b0) or a solvent solution in advance in (X0) before the monomer is dispersed. 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). The following (1), (2), etc. are mentioned as a combination of the reactive group which a reactive group containing prepolymer ((alpha)) and a hardening | curing agent ((beta)).
(1): The reactive group of the reactive group-containing prepolymer (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and the curing agent (β) is an active hydrogen group-containing compound (β1). There is a combination.
(2) The reactive group-containing prepolymer (α) has an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) capable of reacting with an active hydrogen-containing group. combination.
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 components is such that the ratio of the polyol (1) and the polycarboxylic acid (2) is the molar ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. ] Is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.3 / 1 to 1.02 / 1. In the case of other skeletons and end group prepolymers, the ratios are the same except that the constituent components are changed. In the 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 the isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate, the ratio of the polyisocyanate is an isocyanate group [NCO], The molar ratio [NCO] / [OH] of the hydroxyl group [OH] of the hydroxyl group-containing polyester is usually 5/1 to 1/1, preferably 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1. 1.5 / 1. In the case of prepolymers having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

  The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. By setting it as the said range, the molecular weight of the hardened | cured material obtained by making it react with a hardening | curing agent ((beta)) becomes high. The number average molecular weight of the reactive group-containing prepolymer (α) is usually 500 to 30,000, preferably 1,000 to 20,000, more 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 usually not more than 2,000 poise, preferably not more than 1,000 poise at 100 ° C. By setting it to 2,000 poise or less, it is preferable in that resin particles (C) having a sharp particle size distribution can be obtained with a small amount of solvent.

  Examples of the active hydrogen group-containing compound (β1) include polyamine (β1a), polyol (β1b), polymercaptan (β1c) and water (β1d) which may be blocked with a detachable compound. Among these, preferred are (β1a), (β1b) and (β1d), more preferred are (β1a) and (β1d), and particularly preferred are blocked polyamines and (β1d ). (Β1a) is exemplified by those similar to polyamine (16). Preferred as (β1a) are 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, 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 dicarboxylic acid (13), and examples of the polycarboxylic acid include those similar to the polycarboxylic acid (5), and preferable ones are also the same.

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

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

  When the combination of the prepolymer (α) having a reactive group and the curing agent (β) is used as the precursor (b0), the method of polymerizing (b0) in the dispersion (X2) of the fine particles (C2) is particularly limited. However, a method of mixing (α) and (β) immediately before dispersing (b0) or a solvent solution thereof in (X0) and dispersing them at the same time as the polymerization reaction is preferable. The polymerization reaction time is selected depending on the reactivity depending on the combination of the reactive group structure of the prepolymer (α) and the curing agent (β), and is preferably 5 minutes to 24 hours. The reaction may be completed in (X2) before depressurization, or may be allowed to react to some extent in (X2), depressurized and (C) is taken out, and then aged in a thermostat 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 polymerization temperature is preferably 30 to 100 ° C, more preferably 40 to 80 ° C.

   When the solvent solution of the precursor (b0) is used, the same solvent as that used in the second invention can be used at the same concentration as the solvent.

  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 usually 3,000 or more, preferably 3,000 to 10,000,000, more preferably 5,000 to 5,000. One million.

  In addition, a reactive group-containing prepolymer (α) and a polymer that does not react with the curing agent (β) during reaction of the reactive group-containing prepolymer (α) with the curing agent (β) [so-called dead polymer] 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.

Next, the manufacturing method of the resin particle (C) which is preferable 3rd invention is demonstrated.
In a preferred third invention, a molten solution of resin (b) or a solvent solution of resin (b) containing a dispersion stabilizer (D) having at least one of a dimethylsiloxane group and a functional group containing fluorine, The pressure of the dispersion (X3) of the fine particles (C3) obtained by dispersing in the dispersion (X02) composed of the fine particles (A) and carbon dioxide (X) in a liquid or supercritical state is reduced to a pressure. By removing the medium (X) from the dispersion medium (X3), resin particles (C) are obtained.

  In a preferred third invention, the dispersion stabilizer (D) is not added to the carbon dioxide (X) side as in the preferred first invention, but a molten solution of the resin (b) or a solvent solution of the resin (b). Add to. The dispersion stabilizer (D) used here can be the same as that of the preferred first invention, but is preferably compatible with the resin (b) or the solvent solution of the resin (b). Otherwise, operations similar to those of the preferred first invention can be used.

Next, the manufacturing method of the resin particle (C) which is preferable 4th invention is demonstrated.
In a preferred fourth invention, a precursor (b0) of a resin (b) or a solvent solution thereof containing a dispersion stabilizer (D) having at least one of a dimethylsiloxane group and a functional group containing fluorine is added to fine particles. In the dispersion (X4) of fine particles (C4) obtained by dispersing in (A) and the dispersion (X02) comprising carbon dioxide (X) in liquid or supercritical state, (b0) is subjected to the polymerization reaction The resin particles (C) are obtained by removing the medium (X) from the dispersion medium (X4) by reducing the pressure.
In a preferred fourth invention, the resin (b) precursor (b0) or a solvent solution thereof is used instead of the resin (b) melt or the resin (b) solvent solution of the preferred third invention, Operations similar to those of the preferred third invention can be used except that (b0) is polymerized in the dispersion (X4).

  The resin particles (C) of the present invention can be obtained by changing the particle size of the fine particles (A) and the resin particles (B) and the surface coverage of the resin particles (B) with the fine particles (A). Can be granted. 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 BET specific surface area of (C) is preferably 0.5 to 5.0 m2 / g. The BET specific surface area of the present invention 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 (C) is preferably 0.01 to 0.8 μm. Ra is a value obtained by arithmetically averaging the absolute value of the deviation between the roughness curve and its center line, and can be measured by, for example, a scanning probe microscope system (manufactured by Toyo Technica).

  The resin particles (C) of the present invention are hydrophobic because they have a sharp particle size distribution and do not contain water-soluble surfactants or ionic substances. Therefore, the resin particles (C) can be used for coating additives, adhesive additives, cosmetic additives, paper coating additives, slush molding resins, powder coatings, spacers for manufacturing electronic components, catalysts. It is useful as a carrier for medical use, electrophotographic toner, electrostatic recording toner, electrostatic printing toner, standard particles for electronic measuring instruments, particles for electronic paper, medical diagnostic carrier, chromatographic filler, particles for electrorheological fluid, and the like.

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” represents parts by weight and “%” represents% by weight.

Production Example 1 <Preparation of Metal Soap Dispersion>
In an autoclave equipped with a stirrer, 700 parts of normal hexane, 240 parts of magnesium distearate (A-1), 20 parts of decanoic acid, carboxyl-modified silicone (D-1) represented by the following formula (functional group equivalent: 2,300) 40 parts were mixed and stirred at 85 ° C. until the magnesium distearate was completely dissolved, and then cooled to 30 ° C. to obtain [Metal Soap Dispersion] (X′0-1). It was 0.3 micrometer when the volume average particle diameter of the dispersion liquid was measured with the laser scattering type particle size distribution analyzer (LA920: made by Horiba Seisakusho).
Structure of carboxyl-modified silicone (D-1):
HOOC (CH ₂ ) ₃ (CH ₃ ) ₂ SiO ((CH ₃ ) ₂ SiO) _n Si (CH ₃ ) ₂ (CH ₂ ) ₃ COOH (functional group equivalent: 2,000)

Production Example 2 <Preparation of Silica Dispersion>
In a container equipped with a stirrer, 700 parts of normal hexane, fumed silica (Aerosil R974: manufactured by Nippon Aerosil Co., Ltd.) (A-2) 295 parts, [Amino Modified Silicone 1] (D-2) 15 parts are mixed, and a bead mill ( Dispersed for 5 hours with a Dynomill MultiLabo (manufactured by Shinmaru Enterprises) to obtain [silica dispersion] (X′0-2). It was 0.13 micrometer when the volume average particle diameter of the dispersion liquid was measured with the laser scattering type particle size distribution analyzer (LA920: made by Horiba Seisakusho).
[Amino-modified silicone 1] (D-2) structure:
(CH ₃ ) ₃ SiO ((CH ₃ ) ₂ SiO) _n Si (CH ₃ ) ₂ (CH ₂ ) ₃ NH ₂
(Functional group equivalent: 2,200)

Production Example 3 <Preparation of Polyester Solution>
Into a reaction vessel equipped with a stirrer and a dehydrator, 218 parts of bisphenol A / EO 2 mol adduct, 537 parts of bisphenol A / PO 3 mol adduct, 213 parts of terephthalic acid, 47 parts of adipic acid and 2 parts of dibutyltin oxide are added. Then, after dehydration reaction at 230 ° C. under normal pressure for 5 hours, dehydration reaction was performed under reduced pressure of 3 mmHg for 5 hours. The mixture was further cooled to 180 ° C., 43 parts of trimellitic anhydride was added, and the reaction was performed at normal pressure for 2 hours to obtain [Polyester 1] (b-1). [Polyester 1] had a Tg of 44 ° C., Mn of 2700, Mw of 6500, and an acid value of 25. Further, 400 parts of [Polyester 1] was dissolved in 600 parts of acetone to obtain [Polyester 1 solution].

Production Example 4 <Preparation of Prepolymer Solution>
In a reaction vessel equipped with a stirrer and a dehydrator, bisphenol A · EO 2 mol adduct 6
81 parts, 81 parts of bisphenol A / PO2 molar adduct, 275 parts of terephthalic acid, 7 parts of adipic acid, 22 parts of trimellitic anhydride, 2 parts of dibutyltin oxide are added, and dehydration reaction is performed at normal pressure and 230 ° C. for 5 hours. Then, dehydration reaction was performed for 5 hours under a reduced pressure of 3 mmHg to obtain [Polyester 2]. [Polyester 2] had a Tg of 54 ° C., Mn of 2200, Mw of 9500, an acid value of 0.8, and a hydroxyl value of 53. Furthermore, 350 parts of [Polyester 2], 50 parts of isophorone diisocyanate, and 600 parts of acetone were put into an autoclave and reacted at 100 ° C. for 5 hours in a sealed state to obtain a [prepolymer solution] having an isocyanate group at the molecular end. . [Prepolymer] (b0-1) had an NCO content of 1.5%.

Production Example 5 <Preparation of dispersion stabilizer>
In a reaction vessel equipped with a thermometer, a stirrer, a cooling tube, and a nitrogen introduction tube, 139 parts of normal hexane was charged, and the atmosphere was replaced with nitrogen, followed by heating to 70 ° C. with stirring. Subsequently, a mixture of 25 parts of perfluorooctylethyl methacrylate, 55 parts of styrene and 20 parts of butyl acrylate, and a mixture of 10 parts of normal hexane and 1 part of benzoyl peroxide are simultaneously added dropwise over 4 hours, and further 70 ° C. To obtain a [dispersion stabilizer solution] in which [dispersion stabilizer] (D-3) was dissolved in normal hexane. The solid content concentration of the [dispersion stabilizer solution] was 40%.

Production Example 6 <Preparation of Silica Dispersion 2>
In Production Example 2, fumed silica (Aerosil NA-50Y: Nippon Aerosil) (A-3) having an amino group on the surface is used instead of fumed silica (Aerosil R974: manufactured by Nippon Aerosil) (A-2). Except that, [Silica dispersion 2] (X′0-3) was obtained in the same manner as in Production Example 2. It was 0.15 micrometer when the volume average particle diameter of the dispersion liquid was measured with the laser scattering type particle size distribution analyzer (LA920: made by Horiba Seisakusho).

Example 1 (Preferred first invention)
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 10 MPa and 40 ° C. [Polyester 1 (b-1) solution] in the resin solution tank T1, 806 parts of [Metal soap dispersion (X′0-1)] in the fine particle dispersion tank T2, and [Amino-modified silicone 1 (D-2) 194 parts were charged. Next, carbon dioxide is introduced into the dispersion tank T3 from the cylinder B1 and the pump P3, adjusted to 15 MPa and 40 ° C., and [metal soap dispersion (X′0-1)] and [amino modified] from the tank T2 and the pump P2. Silicone 1 (D-2)] mixture was introduced. Next, while stirring the inside of the dispersion tank T3 at 1500 rpm, [the solution of polyester 1 (b-1)] was introduced into the dispersion tank T3 from the tank T1 and the pump P1.

The mass ratio of the composition charged into the dispersion tank T3 is as follows.
[Polyester 1 (b-1) solution] 450 parts of [metal soap dispersion (X′0-1)] and [amino-modified silicone 1 (D-2)] mixture
30 parts carbon dioxide 520 parts The mass of carbon dioxide introduced is the temperature of carbon dioxide (40 ° C.) and pressure (15 MPa).
From this, the density of carbon dioxide was calculated from the state equation described in Document 2 below, and this was multiplied 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 [Polyester 1 (b-1) solution], the mixture was stirred for 1 minute to obtain dispersion (X1). The valve V1 was opened, carbon dioxide previously adjusted to 10 MPa and 40 ° C. was charged into the particle recovery tank T4, a dispersion slurry, that is, a dispersion (X1) was introduced therein, and V1 was closed when the pressure became constant. . By this operation, the solvent was extracted from the resin. Next, carbon dioxide containing the extracted solvent is discharged to the solvent trap tank T5 by holding the pressure at 10 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. Introducing carbon dioxide into the particle recovery tank T4 from the pressure cylinder B2 and the pump P4 stops the introduction of carbon dioxide when 5 times the amount of carbon dioxide introduced into the dispersion tank T3 is introduced into the particle recovery tank T4. did. 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 adjustment valve V2 was opened little by little, and the inside of the particle recovery tank was depressurized to atmospheric pressure to obtain resin particles (C-1) supplemented by the filter F1.

Example 2 (Preferred second invention)
In Example 1, Resin particles (C-2) were obtained in the same manner as in Example 1 except that the following mixed solution was used instead of 450 parts of [Polyester 1 (b-1) solution]. . That is, 845 parts of [Polyester 1 (b-1) solution] and 6 parts of hexamethylenediamine were stirred and mixed for 10 minutes, and then 149 parts of [Prepolymer (b0-1) solution] were mixed. [Polyester 1 (b-1) solution], hexamethylenediamine mixture and [prepolymer (b0-1) solution] were line-mixed and then uniformly mixed with a static mixer. In addition, since reaction advances simultaneously with mixing, operation of the special polymerization process is not performed.
The mass ratio of the composition charged into the dispersion tank T3 in Example 2 is as follows.
[Polyester 1 (b-1) solution], [Prepolymer (b0-1) solution], 450 parts of a mixture of hexamethylenediamine [metal soap dispersion (X′0-1)] and [amino-modified silicone 1] (D-2)]
30 parts carbon dioxide 520 parts

Example 3 (preferred third invention)
In Example 1, instead of [Polyester 1 (b-1) solution], a mixture of [Polyester 1 (b-1) solution] 909 parts and [Amino-modified silicone 2 (D-4)] 91 parts was mixed. In place of the mixture of 806 parts of [metal soap dispersion (X′0-1)] and [amino-modified silicone 1 (D-2)], [metal soap dispersion (X′0-1) ] Was used in the same manner as in Example 1 except that a resin particle (C-3) was obtained. The mass ratio of the composition charged into the dispersion tank T3 in Example 3 is as follows.
Mixture of [Polyester 1 (b-1) solution] and [Amino-modified silicone 2 (D-4)]
450 parts [metal soap dispersion] (X′0-1) 27 parts carbon dioxide 523 parts [amino-modified silicone 2 (D-4)] structure:
(CH ₃ ) ₃ SiO ((CH ₃ ) ₂ SiO) _n ((CH ₃ ) (NH ₂ ) SiO) _m Si (CH ₃ ) ₃
(Functional group equivalent: 2,000)

Example 4 (preferred fourth invention)
In Example 2, instead of the [polyester 1 (b-1) solution], [prepolymer (b0-1) solution] and hexamethylenediamine mixture, [polyester 1 (b-1) solution] 752 Part, [solution of prepolymer (b0-1)] 166 parts, hexamethylenediamine 7 parts, [amino-modified silicone 2 (D-4)] 75 parts, and [metal soap dispersion (X '0-1)] and [amino-modified silicone 1 (D-2)], except that [metal soap dispersion (X'0-1)] was used instead of the mixture. Resin particles (C-4) were obtained. The mass ratio of the composition charged into the dispersion tank T3 in Example 4 is as follows.
[Polyester 1 (b-1) solution], [Prepolymer solution 1 (b0-1)], hexamethylenediamine, [amino-modified silicone 2 (D-4)] mixture
450 parts [metal soap dispersion (X′0-1)] 26 parts carbon dioxide 524 parts

Example 5 [Preferred Third Invention (2)]
In Example 3, resin particles (C--) were used in the same manner as in Example 3 except that [Dispersion stabilizer solution (D-3)] was used instead of [Amino-modified silicone 2 (D-4)]. 5) was obtained. The mass ratio of the composition charged into the dispersion tank T3 in Example 5 is as follows.
Mixture of [polyester 1 (b-1) solution] and [dispersion stabilizer solution (D-3)]
450 parts [metal soap dispersion (X′0-1)] 24 parts carbon dioxide 526 parts

Example 6 [Preferred Third Invention (3)]
Resin particles were obtained in the same manner as in Example 3 except that [Silica dispersion (X′0-2)] was used instead of [Metal soap dispersion (X′0-1)]. (C-6) was obtained. The mass ratio of the composition charged into the dispersion tank T3 in Example 6 is as follows.
Mixture of [Polyester 1 (b-1) solution] and [Amino-modified silicone 2 (D-4)]
450 parts [silica dispersion (X′0-2)] 24 parts carbon dioxide 526 parts

Example 7 [Preferred First Invention (2)]
In the experimental apparatus of FIG. 1, first, the valves V1 and V2 were closed, carbon dioxide was introduced into the particle recovery tank T4 from the cylinder B2 and the pump P4, and the pressure was adjusted to 10 MPa and 40 ° C. Next, [Polyester 1] powder, fumed silica (Aerosil R974: manufactured by Nippon Aerosil Co., Ltd.) (A-2), and [Amino-modified silicone 1 (D-1)] are charged into the dispersion tank T3 in the following mass ratio. Heated to ° C. Next, carbon dioxide was introduced into the dispersion tank T3 from the cylinder B1 and the pump P3, adjusted to 15 MPa and 100 ° C., and the inside of the dispersion tank T3 was stirred at 1500 rpm.

The mass ratio of the composition charged into the dispersion tank T3 is as follows.
[Polyester 1] 250 parts [fumed silica (A-2)] 25 parts [amino-modified silicone 1 (D-2)] 1 part carbon dioxide 717 parts

After stirring for 20 minutes, the valve V1 was opened, the pressure regulating valve V2 was opened little by little, and the inside of the particle recovery tank was depressurized to atmospheric pressure to obtain resin particles (C-7).

Example 8 [Preferred Third Invention (5)]
Resin particles were obtained in the same manner as in Example 6 except that [Silica dispersion 2 (X′0-3)] was used instead of [Silica dispersion (X′0-2)]. (C-8) was obtained.

Comparative Example 1
Resin particles (C-9 ′) were obtained in the same manner as in Example 3 except that [Metal soap dispersion (X′0-1)] was not charged in Example 3.

Comparative Example 2
Resin particles (C-10 ′) were obtained in the same manner as in Example 4 except that [Metal soap dispersion (X′0-1)] was not charged in Example 4.

Comparative production example 1
A reaction vessel equipped with a stirrer and a thermometer was charged with 683 parts of water, 11 parts of a sodium salt of an ethylene oxide methacrylate adduct sulfate, 139 parts of styrene, 138 parts of methacrylic acid, and 1 part of ammonium persulfate at 400 rpm. And stirring for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt) [polymer A fine particle dispersion] was obtained. The volume average particle diameter of the [polymer fine particle dispersion] measured by LA-920 was 0.15 μm. A part of the [polymer fine particle dispersion] was dried to isolate the resin component. The resin content Tg was 154 ° C.

Comparative production example 2
784 parts of water, 136 parts of [polymer fine particle dispersion], and 80 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate were mixed and stirred to obtain a milky white liquid. This is referred to as an “aqueous dispersion”.

Comparative production example 3
In a reaction vessel equipped with a stir bar and a thermometer, 50 parts of ethylenediamine and 50 parts of MIBK were charged and reacted at 50 ° C. for 5 hours. Let the obtained ketimine compound be a [curing agent].

Comparative Example 3
In a beaker, 150 parts of [prepolymer (b0-1) solution], 6 parts of [curing agent] and 40 parts of ethyl acetate were mixed, and after adding 457 parts of [aqueous dispersion], 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 is put into a reaction vessel equipped with a stirring bar and a thermometer, and the solvent is removed and reacted at 50 ° C. for 10 hours, followed by filtration and drying to obtain resin particles (C-11 ′). It was.

Comparative Example 4
In Example 1, when the same operation as Example 1 was performed except not charging [amino modified silicone 1 (D-2)], the resin particle was not able to be obtained. The resin (b) was adhered to the bottom surface of the dispersion tank T3.

Measurement Example of Physical Properties Resin particles (C-1) to (C-8) and (C-9 ′) to (C-11 ′) obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were replaced with sodium dodecylbenzenesulfonate. Dispersed in an aqueous solution (concentration 0.1%), DNc and DVc were measured with a Coulter counter [Multitizer III (manufactured by Beckman Coulter)]. The surface wettability was measured by the above-described method described in the literature (according to Color Material Association Journal, No. 73 [3], 2000, P132-138). The results are shown in Table 1.

(C-1) to (C-8) were particles having a sharp particle size distribution and low surface wettability. Among these, (C-7) did not use a solvent, so the particle size distribution was slightly poorer than the others. In (C-9 ') and (C-10'), the aggregation of particles progressed and DVc / DNc deteriorated remarkably. In (C-11 '), particles having a sharp particle size distribution were obtained, but the particles had high surface wettability and poor hydrophobicity.

  The resin particles of the present invention include paint additives, cosmetic additives, paper coating additives, slush molding resins, powder coatings, electronic component manufacturing spacers, catalyst carriers, electrophotographic toners, electrostatic recordings. It is extremely useful as toners, electrostatic printing toners, standard particles for electronic measuring instruments, particles for electronic papers, medical diagnostic carriers, chromatographic fillers, particles for electrorheological fluids, and other resin particles for molding materials.

Experimental equipment used to make resin particles

Explanation of symbols

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 (13)

Resin (b) or solvent solution of resin (b), or precursor (b0) of resin (b) or solvent solution thereof is dispersed in carbon dioxide (X) in a liquid or supercritical state, and the pressure is reduced. In the method for producing resin particles by removing carbon dioxide (X) in a liquid or supercritical state, a dispersion stabilizer (D) having at least one of a dimethylsiloxane group and a functional group containing fluorine (D ) And fine particles (A) are used together to obtain resin particles (C) in which the fine particles (A) are adhered to the surfaces of the resin particles (B) made of the resin (b). . Dispersion formed by dispersing fine particles (A) in liquid or supercritical carbon dioxide (X) containing a dispersion stabilizer (D) having at least one of a dimethylsiloxane group and a functional group containing fluorine. Dispersion of resin particle (C1) dispersion (X1) obtained by dispersing resin (b) melt or resin (b) solvent solution in medium (X0) by reducing the pressure. Resin particles (C) in which fine particles (A) are attached to the surface of resin particles (B) made of resin (b) by removing liquid or supercritical carbon dioxide (X) from body (X1) The method for producing resin particles according to claim 1, wherein: Dispersion formed by dispersing fine particles (A) in liquid or supercritical carbon dioxide (X) containing a dispersion stabilizer (D) having at least one of a dimethylsiloxane group and a functional group containing fluorine. In the dispersion (X2) of the resin particles (C2) obtained by dispersing the precursor (b0) of the resin (b) or the solvent solution thereof in the medium (X0), the precursor (b0) is subjected to a polymerization reaction. Thereafter, the surface of the resin particles (B) in which the fine particles (A) are made of the resin (b) by removing the liquid or supercritical carbon dioxide (X) from the dispersion (X2) by reducing the pressure. The method for producing resin particles according to claim 1, wherein resin particles (C) adhered to the resin particles are obtained. The resin (b) melt or the resin (b) solvent solution containing the dispersion stabilizer (D) having at least one of a dimethylsiloxane group and a fluorine-containing functional group, the fine particles (A) are liquid Alternatively, by dispersing the dispersion (X3) of resin particles (C3) obtained by dispersing in a dispersion medium (X02) dispersed in carbon dioxide (X) in a supercritical state, the pressure is reduced. Resin particles (C) in which fine particles (A) are adhered to the surface of resin particles (B) made of resin (b) by removing carbon dioxide (X) in a liquid or supercritical state from dispersion (X3) The method for producing resin particles according to claim 1, wherein: Resin (b) precursor (b0) or solvent solution thereof containing a dispersion stabilizer (D) having at least one of a dimethylsiloxane group and a fluorine-containing functional group, the fine particles (A) are liquid or Polymerization reaction of precursor (b0) in dispersion (X4) of resin particles (C4) obtained by dispersion in dispersion medium (X02) dispersed in carbon dioxide (X) in a supercritical state After that, by removing the carbon dioxide (X) in a liquid or supercritical state from the dispersion (X4) by reducing the pressure, the fine particles (A) of the resin particles (B) made of the resin (b) The method for producing resin particles according to claim 1, wherein the resin particles (C) adhered to the surface are obtained. The dispersion (X1) or dispersion (X3) obtained by dispersing the solvent solution of the resin (b) is further mixed with liquid or supercritical carbon dioxide (X) to obtain resin particles (C1) or resin. The solvent is extracted from the particles (C3) into a carbon dioxide phase, the carbon dioxide containing the solvent is further substituted with (X), and then the pressure is reduced to obtain resin particles (C1) or resin particles (C3). The manufacturing method of any one of Claims 1, 2, and 4. In the dispersion (X2) or dispersion (X4) obtained by dispersing the solvent solution of the precursor (b0) of the resin (b), the precursor (b0) is polymerized and then dispersed (X2) or dispersion. The body (X4) is further mixed with carbon dioxide (X) in a liquid or supercritical state, and the solvent is extracted from the resin particles (C2) or the resin particles (C4) into a carbon dioxide phase. Furthermore, after substituting with (X), the manufacturing method of any one of Claim 1, 3, 5 which obtains the resin particle (C2) or the resin particle (C4) by making pressure reduced. The acid value of resin (b) is 1-50, and dispersion stabilizer (D) has an amino group, The manufacturing method of any one of Claims 1-7 characterized by the above-mentioned. The production method according to claim 1, wherein the resin (b) is at least one resin selected from the group consisting of a urethane resin, a polyester resin, and an epoxy resin. The precursor (b0) of the resin (b) is a mixture of a reactive group-containing prepolymer (α) and a curing agent (β), according to any one of claims 1, 3, 5, 7, 8, and 9. Manufacturing method. The reactive group-containing prepolymer (α) has at least one reactive group selected from the group consisting of an isocyanate group, a blocked isocyanate group and an epoxy group, and the curing agent (β) has an active hydrogen group. The manufacturing method according to claim 10. Fine particles (A) are metal oxide, metal hydroxide, metal carbonate, metal sulfate, metal silicate, metal nitride, metal phosphate, metal borate, metal titanate, metal sulfide, At least one selected from the group consisting of at least one inorganic fine particle (A1) selected from the group consisting of carbons, urethane resin, epoxy resin, vinyl resin, polyester resin, melamine resin, benzoguanamine resin, fluororesin, and silicone resin. Selected from the group consisting of seed organic resin fine particles (A21), long chain fatty acid metal salt fine particles (A23), or inorganic fine particles (A1), organic resin fine particles (A21) and long chain fatty acid metal salt fine particles (A23). It is a mixture of at least 2 sorts, The manufacturing method of any one of Claims 1-11. The acid value of resin (b) is 1-50, and microparticles | fine-particles (A) have an amino group on the particle | grain surface, The manufacturing method of any one of Claims 1-12 characterized by the above-mentioned.

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