JP2010155943A - Method for producing resin particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain resin particles which have no surface-active substance or solvent remaining within the resin particles or at their surfaces and exhibit a sharp particle size distribution. <P>SOLUTION: A method for producing the resin particles (C), prepared by depositing particulates (A) on the surface of resin particles (B), comprises: a step of sorting resin particles (C1), in which the particulates (A) are deposited on the surfaces of the resin particles (B) containing a resin (b), in a dispersion (X1) of the resin particles (C1), provided that the dispersion (X1) is obtained by dispersing a melt solution of the resin (b) or a solvent solution of the resin (b) in a dispersion medium (X0) that contains liquid or supercritical carbon dioxide (X) and a solvent (S) and in which the particulates (A) are dispersed; and a step of removing (X) and (S). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing resin particles. More specifically, the present invention relates to a method for producing 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, it is possible to obtain particles having a fine particle size and a sharp particle size distribution. 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 method for forming particles in a non-aqueous medium, there is a method in which a resin melted by heating in a supercritical fluid is mechanically dispersed to form fine particles and then reduced in pressure to obtain resin particles (for example, see Patent Document 2). Are known
JP-A-9-319144 JP-A-2005-107405

According to the method of obtaining resin particles by mechanically dispersing the heat-melted resin in the supercritical fluid and then reducing the pressure to obtain resin particles, the surface active substance is contained in the resin particles without the need for a hydrophilic component. Since it does not remain on the surface, it is possible to obtain particles having excellent powder characteristics, electrical characteristics, etc., but 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 the surface active substance and the solvent do not remain 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 is the following two inventions.
(I) Dispersion medium containing liquid or supercritical carbon dioxide (X) and solvent (S) in which fine particles (A) are dispersed in a melt of resin (b) or a solvent solution of resin (b) In a dispersion (X1) of resin particles (C1) obtained by dispersing in (X0), the fine particles (A) adhere to the surface of the resin particles (B) containing the resin (b). ) And a process for removing (X) and (S), and a method for producing resin particles (C) in which fine particles (A) are attached to the surfaces of resin particles (B) .
(II) A dispersion medium containing a precursor (b0) of resin (b) or a solvent solution thereof containing liquid carbon dioxide (X) in which fine particles (A) are dispersed or supercritical carbon dioxide (X) and a solvent (S) ( Dispersion (X2) of resin particles (C2) obtained by dispersing in (X0) and reacting (b0) and having fine particles (A) adhered to the surface of resin particles (B) containing resin (b) ) In which the fine particles (A) are attached to the surfaces of the resin particles (B), the method comprising the steps of classifying (C2) and removing (X) and (S) The manufacturing method of (C).

  The resin particles obtained by the production method of the present invention do not contain a surfactant having a hydrophilic group (surfactant, polymer protective colloid, surfactant fine particles, etc.) and a solvent, and the particle size distribution is very sharp. Resin particles. 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, 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. Specific examples of the composition (A21) include those similar to the resin (b) described later. 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 Organic wax fine particles (A22) such as a mixture of the above, and metal salt fine particles (A23) of long-chain fatty acids. 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, And 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 at least one selected from the group consisting of at least one organic resin fine particle (A21) and long-chain fatty acid metal salt fine particles (A23).

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

  A preferred weight ratio of the fine particles (A), carbon dioxide (X), and solvent (S) in the dispersion medium (X0) (the total is 100) is (A) / (X) / (S) [weight ratio]. = (5-40) / (30-60) / (20-50). When (A), (X), and (S) in (X0) are in this range, resin particles (C) having a sharp particle size can be obtained.

  The resin particle (B) contains 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 polyurethane resin, an epoxy resin, a vinyl 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 of the polyol and the polycarboxylic acid is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1 as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1/1, particularly preferably 1.3 / 1 to 1.02 / 1.

Diol (11) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, Tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol) An alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; an alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above bisphenol; Examples include polylactone diol (such as poly ε-caprolactone diol) and polybutadiene diol. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. Examples of the trihydric or higher polyol (12) include 3 to 8 or higher polyhydric aliphatic alcohols (such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol); trisphenols (such as trisphenol PA) ); Novolak resins (phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trisphenols; alkylene oxide adducts of the above 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 polyisocyanate, aromatic aliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, Oxazolidone group-containing modified products) and mixtures of two or more thereof. Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 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 the polyamine (16) include aliphatic polyamines (C2 to C18): (1) aliphatic polyamine {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) , Polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; (2) these alkyls (C1-C4 ) Or substituted hydroxyalkyl (C2-C4) [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexa Methylenediamine, methyliminobispropylamine, etc.]; (3) Alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5, 5] Undecane etc.]; (4) Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine etc.), alicyclic polyamines (C4 to C15): 1,3- Heterocyclic polyamines (C4-C15) such as diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline): piperazine, N-aminoethylpiperazine, 1,4- Aromatics such as diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine Reamines (C6-C20): (5) Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethane Diamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ', Aromatic polyamines having 4 ″ -triamine, naphthylenediamine, etc .; nucleus-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, Crudetolylenediamine, Diethyltolylenediamine 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 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- , 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-diaminodiph Nylmethane, 3,3′-diethyl-2,2′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diamino Benzophenone, 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; methoxy; An aromatic polyamine having methylene bis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-alkyl, etc. 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, (4-amino-3-methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4'-methylenebis (2-bromoaniline), 4,4'-methylenebis (2-fluoroaniline) ), 4-aminophenyl-2-chloroaniline, etc.]; (7) Aromatic polyamine having a secondary amino group [a part or all of —NH ₂ of the aromatic polyamine of (4) to (6) above − NH-R '(R' is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4'-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4 -Aminobenzene etc.], polyamide polyamines: dicarboxylic acids (eg dimer acids) and excess polyamines (more than 2 moles per mole of acid) And low molecular weight polyamide polyamines obtained by condensation with a realkylene polyamine, etc., and polyether hydrides of polyether polyamines: polyether polyols (polyalkylene glycols, etc.).

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

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

  The polyepoxide (18) used for this invention will not be specifically limited if it has two or more epoxy groups in a molecule | numerator. What has preferable 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material as a preferable polyepoxide (18). The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide (18) is preferably 65 to 1000, and more preferably 90 to 500. When the epoxy equivalent is 1000 or less, the cross-linked structure is strengthened and the physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are improved. On the other hand, it is easy to synthesize one having an epoxy equivalent of 65 or more. It is.

  Examples of the polyepoxide (18) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols. Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl di Glycidyl ether, tetramethylbiphenyl diglycidyl 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. Further, in the present invention, as the aromatic system, P-aminophenol triglycidyl ether, tolylene diisocyanate or a diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, obtained by reacting a polyol with the reaction product. Also included are diglycidyl ethers of glycidyl group-containing polyurethane (pre) polymers and alkylene oxide (ethylene oxide or propylene oxide) adducts of bisphenol A. Examples of the heterocyclic polyepoxy compound include trisglycidylmelamine; examples of the alicyclic polyepoxy compound include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, and bis (2,3-epoxycyclopentyl). Ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-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 polyhydric 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 system also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more polyepoxides may be used in combination.

  The number average molecular weight (measured by GPC, hereinafter abbreviated as Mn) of the resin (b) is preferably 2 to 5 million, more preferably 2,000 to 500,000, and the SP value is preferably 7 to 18, more preferably. Is 8-14. The Mn of the resin (b) may be suitably adjusted within a preferable range depending on the use. For example, when used for a powder coating, it is preferably 2,000 to 500,000, more preferably 4,000 to 200,000, and the toner for electrophotography. When used, it is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000. When it is desired to improve the heat resistance, water resistance, chemical resistance, particle size uniformity, etc. of the resin particles (C), a crosslinked structure may be introduced into the resin (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. When the crosslinked structure is introduced into the resin (b), the molecular weight between crosslinking points is preferably 30 or more, and more preferably 50 or more.

The glass transition temperature (Tg) of the resin (b) is preferably 0 ° C to 300 ° C, more preferably 20 ° C to 250 ° C. Within this range, problems such as deterioration in storage stability of the particles do not occur. In addition, Tg in this invention is a value calculated | required from DSC measurement.
The Tg of the resin (b) is preferably adjusted according to the application. For example, when used for a powder coating, it is preferably 0 ° C. to 200 ° C., more preferably 35 ° C. to 150 ° C., when used for an electrophotographic toner. The temperature is preferably 20 ° C to 300 ° C, more preferably 80 ° C to 250 ° C.

  The resin particles (C) obtained by the production method of the present invention are particles in which the fine particles (A) are attached 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 preferably 0.001 to 0.1, more preferably 0.002 to 0.00. 08, particularly preferably 0.003 to 0.06, most preferably 0.01 to 0.05. Within the above range, (A) is efficiently adsorbed on the surface of (B), and the resulting particle size distribution of (C) 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. The volume average particle size of (A) is generally preferably 0.0005 to 4 μm, and more preferably 0.001 to 3 μm. However, 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 0.001 to 0.2 μm, and 10 μm resin particles ( When C) is obtained, preferably 0.005 to 3 μm, particularly preferably 0.05 to 2 μm, and 20 μm when resin particles (C) are desired, preferably 0.05 to 4 μm, particularly preferably Is 0.1 to 3 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.), Multisizer III (Beckman).・ Measured by Coulter, Inc.

The volume average particle diameter of the resin particles (C) obtained by the production method of the present invention is preferably 1 to 20 μm, more preferably 1.5 to 10 μm, and particularly preferably 2.5 to 8 μm. When it is 1 μm or more, the handling property as a powder is good. When it is 20 μm or less, the particle size distribution is improved.
The ratio DVc / DNc of the volume average particle size DVc of (C) and the number average particle size DNc of (C) is preferably 1.0 to 1.2, more preferably 1.0 to 1.15, particularly preferably. 1.0 to 1.1. When it is 1.2 or less, powder characteristics (fluidity, charging uniformity, etc.) are remarkably improved.

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

  From the viewpoints of particle size uniformity, storage stability and the like of the resin particles (C), the resin particles (C) are preferably 0.01 to 50% by weight of (A) and 50 to 99.99% by weight of (B And more preferably 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 or the like.

In the production method of the present invention, a melt of the resin (b) or a solvent solution of the resin (b) is added to the liquid or supercritical carbon dioxide (X) and the solvent (S) in which the fine particles (A) are dispersed. Any method may be used as a method of dispersing in the contained dispersion medium (X0).
A specific example is a method in which a solvent solution of resin (b) is sprayed into (X0) via a spray nozzle to form droplets, the resin in the droplets is supersaturated, and resin particles are precipitated. (Known as ASES: Aerosol Solvent Extraction System). Resin solution, high-pressure gas such as (X0), entrainer, etc. are simultaneously ejected from separate pipes from coaxial multiple pipes (double pipes, triple pipes, etc.) to promote the breakup by applying external stress to the droplets. Particles can also be obtained (known as SEDS: Solution Enhanced Dispersion by Supercritical Fluids). In addition, the method of irradiating an ultrasonic wave and the method of using a high-speed disperser are mentioned.

  In this way, the resin (b) is dispersed in the dispersion medium (X0), and the dispersed resin (b) is grown while adsorbing the fine particles (A) on the surface. Resin particles (C1) having fine particles (A) attached to the surface are formed. A dispersion in which (C1) is dispersed in (X) is referred to as dispersion (X1).

  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).

  The temperature of the dispersion medium (X0) and the dispersion (X1) is preferably 30 ° C. or higher in order to prevent carbon dioxide from undergoing a phase transition in the pipe during solidification and block the flow path. In order to prevent thermal deterioration of A), the resin particles (B), and the resin particles (C), 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 pressure in the container forming the dispersion medium (X0) and the dispersion (X1) is preferably 7 MPa or more in order to favorably disperse (C) in carbon dioxide (X). To preferably 40 MPa or less. 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 temperature and pressure of (X0) and (X1) are preferably set within a range in which the resin (b) does not dissolve in (X) and (b) can be aggregated and united. 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 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 (S). The concentration of (b) in the solvent solution of resin (b) is preferably 10 to 90% by weight, more preferably 20 to 80% by weight.

  Examples of the solvent (S) 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 or ester ether solvents; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, Ketone solvents such as ruisobutyl ketone, di-n-butyl ketone, cyclohexanone; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, 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.

  In the supercritical carbon dioxide (X) used in the present invention, another substance (e) is added to adjust the physical property values (viscosity, diffusion coefficient, dielectric constant, solubility, interfacial tension, etc.) as a dispersion medium. For example, nitrogen, helium, argon, an inert gas such as air, water, and the like may be included. The weight (purity) of carbon dioxide in (X) is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.

  In the dispersion (X1) of resin fine particles (C1) in the present invention, the step of classifying (C1) and the step of removing (X) and the solvent (S) are (1) filtration with a filter, (2) centrifugation Classification by the method and solvent removal can be mentioned.

  The filter used for filtration by the filter is not particularly limited, and the material is metal, baked metal, ceramic, polypropylene, polyamide, polyester, polycarbonate, polytetrafluoroethylene, polyvinylidene chloride, polyphenylene sulfide, cellulose, glass, etc. Can be mentioned.

  Examples of the shape of the filter include a porous body, a mesh, and a cloth. In the case of meshes and cloths, weaving methods such as plain weave, twill weave, satin weave, and twist weave are listed. The mesh opening is arbitrarily selected so as to obtain a desired particle diameter, but is preferably 0.1 to 25 μm, more preferably 1 to 15 μm, and most preferably 3 to 8 μm. When it is desired to remove resin particles larger than the desired particle size, the resin particles (C) having the desired particle size pass, and the coarse powder may be left on the filter, and small resin particles should be removed. In that case, the resin particles (C) having a desired particle diameter may remain on the filter, and the fine powder may pass through the filter. Also, when removing coarse particles and fine powder, remove coarse particles with a filter with a large opening, and remove fine powder with a filter with a small opening so that the DVc / DVn of the resin particles (C) is in a preferred range. I can do it.

  As a specific method of filtration using a filter, a filter is set in advance in a container that forms the dispersion medium (X0) and (X1) or a pipe connected to the container, and the dispersion medium (X0) and (X1) The pressure difference is reduced to another container filled with carbon dioxide at a pressure 0.5 to 3.0 MPa, preferably 0.8 to 2.0 MPa, most preferably 1.0 to 1.5 MPa lower than the container to be formed. The resin particles (C) can be filtered by transferring (X1) while blowing carbon dioxide into a container for forming the dispersion media (X0) and (X1) so as to be constant. By setting the filter excluding the fine powder, the resin particles (C) remain in the filter in the container forming the dispersion medium (X0) and (X1) or in the pipe connected to the container. If a filter excluding coarse powder is set, the resin particles (C) remain in another container filled with carbon dioxide. In this case, by preparing another container and setting the filter excluding fine powder under the same conditions as described above, the resin particles (C) from which both coarse powder and fine powder have been removed remain in the filter. Become.

  As a method of classification and solvent removal by a centrifugal method, there is a method of supplying (X1) into a rotating body, solid-liquid separation by centrifugal force, and continuously discharging the separated liquid. Classification can be performed by making the separated liquid contain fine powder by optimizing the supply amount and the rotation speed.

The centrifugal force of the centrifugation treatment is preferably 100 to 5000G, more preferably 500 to 4000G. When the centrifugal force is 100 G or more, the resin particles are sufficiently separated and the yield is improved. Moreover, when it is 5000 G or less, the amount of fine powder mixed in is reduced, and sufficient classification is possible.
The centrifuge used is not particularly limited as long as it exhibits the above centrifugal force. As the centrifugal separator, a pressure plate-processed separator plate type, cylindrical type, decanter type or the like can be used, and batch type or continuous type devices can also be used, respectively.

  The pressure for favorably performing classification and solvent removal by centrifugation is preferably 5 MPa or more, and preferably 20 MPa or less from the viewpoint of equipment cost and operation cost. More preferably, it is 5.5-15 MPa, Most preferably, it is 6-10 MPa. The temperature is preferably 100 ° C. or lower, and preferably 10 ° C. or higher from the viewpoint of solvent removal efficiency. More preferably, it is 15-70 degreeC, Most preferably, it is 20-60 degreeC.

  The precursor (b0) of the resin (b) used in the present invention is not particularly limited as long as it can be converted into the resin (b) by a chemical reaction. For example, 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, In the case of (epoxy resin, polyester resin), (b0) is exemplified by a combination of a prepolymer (α) having a reactive group and a curing agent (β).

  When a vinyl monomer is used as the precursor (b0), (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], etc.

  (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). The combination.
(2) A combination in which the reactive group of the reactive group-containing prepolymer (α) is an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) that can react with the active hydrogen-containing group. .
In the combination (1), the functional group (α1) capable of reacting with the active hydrogen compound includes an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (α1d) and And acid halide groups (α1e). Among these, (α1a), (α1b) and (α1c) are preferable, and (α1a) and (α1b) are particularly preferable. The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent. Examples of the blocking agent include oximes [acetooxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; lactams [γ-butyrolactam, ε-caprolactam, γ-valerolactam Etc.]; C1-C20 aliphatic alcohols [ethanol, methanol, octanol, etc.]; Phenols [phenol, m-cresol, xylenol, nonylphenol, etc.]; Active methylene compounds [acetylacetone, ethyl malonate, ethyl acetoacetate, etc.] Etc.]; basic nitrogen-containing compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.]; and mixtures of two or more thereof. That. Of these, oximes are preferred, and methyl ethyl ketoxime is particularly preferred.

  Examples of the skeleton of the reactive group-containing prepolymer (α) include polyether (αw), polyester (αx), epoxy resin (αy), and polyurethane (αz). 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 the polyester (αx) include a polycondensate of diol (11) and dicarboxylic acid (13), polylactone (a ring-opening polymerization product 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 polyol (1) to polycarboxylic acid (2) is equivalent ratio [OH] / [COOH] of hydroxyl group [OH] and carboxyl group [COOH]. ] Is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1. In the case of other skeleton 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 an isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate, and the ratio of the polyisocyanate is an isocyanate group [NCO]. The equivalent ratio [NCO] / [OH] of the hydroxyl group [OH] of the hydroxyl group-containing polyester is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, particularly preferably 2.5 /. 1 to 1.5 / 1. In the case of prepolymers having other skeletons and 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 preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000. The weight average molecular weight of the reactive group-containing prepolymer (α) is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and particularly preferably 4,000 to 20,000. The viscosity of the reactive group-containing prepolymer (α) is preferably 200 Pa · s or less, more preferably 100 Pa · s or less, at 100 ° C. Setting it to 200 Pa · s or less is preferable in that resin particles (C) having a sharp particle size distribution can be obtained.

  Examples of the active hydrogen group-containing compound (β1) include polyamine (β1a), polyol (β1b), polymercaptan (β1c) and water (β1d) which may be blocked with a detachable compound. Of these, (β1a), (β1b) and (β1d) are preferable, and (β1a) and (β1d) are more preferable, and particularly preferable 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 preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and particularly preferably 1.2 / 1 to 1 / 1.2. When the curing agent (β) is water (β1d), water is treated as a divalent active hydrogen compound.

  When the combination of the prepolymer (α) having a reactive group and the curing agent (β) is used as the precursor (b0), the method of reacting (b0) in the dispersion (X2) of the resin particles (C2) is particularly limited. However, a method of mixing (α) and (β) immediately before dispersing (b0) or its solvent solution in (X0) and reacting at the same time as dispersing is preferred. Although reaction time is selected by the reactivity by the structure of the reactive group which prepolymer ((alpha) has), and the combination of a hardening | curing agent ((beta)), Preferably it is 5 minutes-24 hours. The reaction may be completed in (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 reaction 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 solvent solution of the resin (b) can be used at the same concentration.

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

  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 (dead polymer).

  Resin (b) precursor (b0) or a solvent solution thereof in a dispersion medium (X0) containing carbon dioxide (X) and solvent (S) in a liquid or supercritical state in which fine particles (A) are dispersed. And (b0) is reacted to obtain a dispersion (X2) of resin particles (C2) in which the fine particles (A) adhere to the surface of the resin particles (B) containing the resin (b), and In the dispersion (X2), the method of classifying (C2) and the method of removing (X) and (S) are performed by using a melt of the resin (b) or a solvent solution of the resin (b). This is the same as the method for obtaining the dispersion (X1) of the particles (C1), the method for classifying (C1) in (X1), and the method for removing (X) and the solvent (S).

The resin particles (C) obtained by the production method of the present invention are obtained by changing the particle diameters of the fine particles (A) and the resin particles (B) and the coverage of the resin particles (B) by the fine particles (A). Desirable irregularities can be imparted to the surface. Furthermore, by controlling the temperature and pressure during decompression, a porous body having bubbles inside can be obtained, and the specific surface area can be increased. When it is desired to improve the powder fluidity, the BET specific surface area of (C) is preferably 0.5 to 5.0 m ² / g. The BET specific surface area in the present invention is measured using a specific surface area meter such as QUANTASORB (manufactured by Yuasa Ionics) (measuring 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 shape of the resin particles (C) is preferably spherical from the viewpoint of powder flowability, melt leveling properties and the like. In that case, the fine particles (A) and the resin particles (B) are also preferably spherical. In (C), Wadell's practical sphericity is preferably 0.85 to 1.00. The Wadell practical sphericity is obtained from a ratio of a diameter of a circle having an area equal to the projected area of the particle and a diameter of a circle having a minimum area circumscribed on the projected image of the particle. The projected image of the particles can be taken by, for example, a scanning electron microscope (SEM).

  The resin particles (C) obtained by the production method of the present invention are hydrophobic because they have a sharp particle size distribution and can be produced so as not to contain a water-soluble surfactant or ionic substance. Therefore, the resin particles (C) can be used for coating additives, cosmetic additives, paper coating additives, slush molding resins, powder coatings, spacers for manufacturing electronic components, catalyst carriers, electrophotographic toners. It is useful for electrostatic recording toner, electrostatic printing toner, standard particles for electronic measuring devices, 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 Silica Suspension (A-1)>
In a container equipped with a stirrer, 700 parts of toluene and 300 parts of fumed silica (Aerosil R974: made by Nippon Aerosil) were mixed and dispersed for 5 hours with a bead mill (Dynomill Multi Labo: made by Shinmaru Enterprises). ] (A-1) was obtained. It was 0.13 micrometer when the average particle diameter of the dispersion liquid was measured with the laser scattering type particle size distribution analyzer (LA920: made by Horiba Seisakusho).

Production Example 2 <Preparation of polymer fine particles (A-2)>
In a vessel equipped with a stirrer and a temperature controller, 238 parts of glycidyl ether of bisphenol A (epoxy equivalent: 190), 62 parts of diaminodiphenylmethane (active hydrogen equivalent 49.5), propylene oxide (5100) to glycerin (92 parts) 700 parts of trifunctional polyether polyol (molecular weight 6,000) to which a mixture of ethylene oxide (800 parts) was added and uniformly mixed, and then heated to 100 ° C. while gently stirring. Thereafter, the reaction temperature was controlled at 100 to 130 ° C. and reacted for 5 hours to obtain a milky white reaction mixture. To this was added 800 parts of methanol, and the mixture was stirred uniformly and filtered. The powder obtained on the filter paper was further washed with methanol and dried to obtain a polymer having an average particle size of 0.8 μm and a glass transition temperature of 165 ° C. Fine particles] (A-2) were obtained.

Production Example 3 <Preparation of polymer fine particles (A-3)>
In a container equipped with a stirrer and a temperature controller, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 139 parts of styrene, 20 parts of divinylbenzene, methacrylic acid When 138 parts of acid, 184 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to form a vinyl resin (styrene salt copolymer of styrene-methacrylic acid-butyl methacrylate-methacrylic acid EO adduct, crosslinkable). An aqueous dispersion was obtained. This aqueous dispersion was freeze-dried to obtain [Polymer fine particles] (A-3) having an average particle size of 0.15 μm and a glass transition temperature of 134 ° C.

Production Example 4 <Preparation of Polyester (b-1) Solution>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 647 parts (24.0 moles) of 1,2-propylene glycol (PG), 688 parts (10.0 moles) of dimethyl terephthalate and a catalyst 3 parts of tetraisopropoxide titanate was added and reacted for 3 hours at 180 ° C. in a nitrogen stream while distilling off the produced methanol. Next, while gradually raising the temperature to 230 ° C., the reaction was carried out for 5 hours while distilling off methanol and an excess amount of PG in a nitrogen stream to obtain terephthalic acid diester. In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 520 parts (10.0 mol) of the terephthalic acid diester obtained above and 353 parts (5.5 mol) of a bisphenol A / propylene oxide 2 mol adduct were obtained. ), 408 parts (5.5 moles) of bisphenol A / propylene oxide 3 mole adduct and 3 parts of tetraisopropoxide titanate as a condensation catalyst were added, and the temperature was raised to 230 ° C. After stirring at 230 ° C. for 1 hour, the reaction was conducted while distilling off propylene glycol under a reduced pressure of 5 to 20 mmHg. The reaction was followed while measuring the viscosity of the polymer to be produced, and taken out when the softening point reached 110 ° C. to obtain [Polyester (b-1)]. The reaction time was 10 hours. [Polyester 1] had a Tg of 60 ° C., a weight average molecular weight of 14,000, and an insoluble content of tetrahydrofuran (hereinafter referred to as THF) of 0%. Furthermore, 500 parts of [polyester (b-1)] was dissolved in 500 parts of toluene to obtain [polyester (b-1) solution].

Production Example 5 <Preparation of Prepolymer (α-1) Solution>
In a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen introduction tube, polybutylene adipate (575 parts) with Mn of 1000, polyhexamethylene isophthalate (383 parts) with Mn of 900, 1-octanol (16.8 parts) ), And after replacing with nitrogen, the mixture was heated to 110 ° C. with melting to melt and cooled to 60 ° C. Subsequently, hexamethylene diisocyanate (242 parts) was added and reacted at 85 ° C. for 6 hours. Next, after cooling to 60 ° C., THF (217 parts), stabilizer (2.5 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and titanium oxide (15.3 parts) [Typaque R- 820 Ishihara Sangyo Co., Ltd.] was added and mixed uniformly to obtain [Prepolymer (α-1) solution]. The obtained [prepolymer (α-1) solution] had an NCO content of 2.2%.

Example 1
In a high-pressure vessel 1 equipped with a stirrer (maximum operating pressure 25 MPa, maximum operating temperature 200 ° C., capacity 10 L, the same applies to other high-pressure vessels), 17 parts of [silica dispersion] (A-1) and 150 parts of methyl ethyl ketone were charged. The pressure was reduced to -0.1 MPa with a vacuum pump. Thereafter, carbon dioxide (purity 99.99%) was introduced, the pressure was adjusted to 10 MPa, the temperature was 40 ° C., and the inside of the container was stirred at a rotation speed of 200 rpm. Further, the [polyester (b-1) solution] was introduced through a capillary (diameter 0.2 mm) at a flow rate of 100 ml / min for 1 minute, allowed to stand for 3 minutes, and then carbon dioxide was flowed at a flow rate of 100 ml / min with a high-pressure pump. And introduced into the high-pressure vessel 1 for 5 minutes. At this time, the high-pressure vessel 1 was held at 10 MPa by a back pressure adjusting valve.
Carbon dioxide was introduced at a flow rate of 100 ml / min for 5 minutes with a high-pressure pump into the high-pressure vessel 1 and another high-pressure vessel 2 connected to the high-pressure vessel 1 having a 8 [mu] m mesh in the pipe and having a valve. At this time, the high-pressure vessel 2 was held at 9 MPa by a back pressure adjusting valve. The valve connecting the high pressure containers 1 and 2 was opened, and the contents of the high pressure container 1 were transferred to the high pressure container 2. At this time, the generated fine particles passed through the mesh, and fine particles of 8 μm or more were cut.
Furthermore, carbon dioxide is introduced for 5 minutes at a flow rate of 100 ml / min with a high-pressure pump into another high-pressure vessel 3 connected to the high-pressure vessel 2 by a pipe having a 3 μm mesh in the pipe and having a valve. did. At this time, the high-pressure vessel 3 was held at 7.5 MPa by a back pressure adjusting valve. The valve connecting the high pressure containers 2 and 3 was opened, and the contents of the high pressure container 2 were transferred to the high pressure container 3. At this time, the generated fine particles passed through the mesh, and fine particles of 3 μm or less were cut. The carbon dioxide and the solvent inside the high-pressure vessel 2 and 3 were discharged from the high-pressure vessel 3 to obtain resin particles (C-1) captured by a filter inside the pipe.

Example 2
In a high-pressure vessel 1 equipped with a stirrer (maximum operating pressure 25 MPa, maximum operating temperature 200 ° C., capacity 10 L), 170 parts of [silica dispersion] (A-1) and 100 parts of decane were charged, and −0.1 MPa with a vacuum pump The pressure was reduced to. Thereafter, carbon dioxide (purity 99.99%) was introduced, the pressure was adjusted to 10 MPa, the temperature was 40 ° C., and the inside of the container was stirred at a rotation speed of 200 rpm. On the other hand, [Prepolymer (α-1) solution] was line-mixed at 98 ml / min and hexamethylenediamine solution (toluene 50% solution) at 2 ml / min, and then via a capillary (diameter 0.2 mm), After introducing the mixture of [prepolymer (α-1) solution] and hexamethylenediamine solution at a flow rate of 100 ml / min for 10 minutes, the mixture was allowed to stand for 3 minutes and then carbon dioxide was flowed at a flow rate of 100 ml / min for 5 minutes with a high-pressure pump. It was introduced into the high-pressure vessel 1. At this time, the high-pressure vessel 1 was held at 10 MPa by a back pressure adjusting valve.
The contents of the high-pressure vessel 1 are transferred to a pressure-resistant decanter connected to the high-pressure vessel 1, carbon dioxide is introduced from the decanter inlet at a flow rate of 100 ml / min so that the pressure is maintained at 6 MPa, and the same amount is discharged from the decanter outlet. Discharged from. After applying a centrifugal force of 3000 G at a temperature of 30 ° C. for 3 minutes, carbon dioxide was discharged to obtain resin particles (C-2).

Example 3
Resin particles (C-3) were prepared in the same manner as in Example 1 except that 10 parts of [Polymer fine particles] (A-2) were used instead of 17 parts of [Silica dispersion] (A-1) in Example 1. Got.

Example 4
Resin particles (C-4) were prepared in the same manner as in Example 2 except that 10 parts of [polymer fine particles] (A-2) were used instead of 17 parts of [silica dispersion] (A-1) in Example 2. Got.

Example 5
Resin particles (C-5) were prepared in the same manner as in Example 1 except that 10 parts of [polymer fine particles] (A-3) were used instead of 17 parts of [silica dispersion] (A-1) in Example 1. Got.

Example 6
Resin particles (C-6) were prepared in the same manner as in Example 2 except that 10 parts of [polymer fine particles] (A-3) were used instead of 17 parts of [silica dispersion] (A-1) in Example 2. Got.

Comparative Example 1
In Example 1, comparative resin particles (RC-1) were obtained in the same manner as in Example 1 except that filter filtration was not performed.

Comparative Example 2
In Example 2, a comparative resin particle (RC-2) was obtained in the same manner as in Example 2 except that the screw decanter was not used.

Measurement Example of Physical Properties Resin particles (C-1) to (C-6), (RC-1), and (RC-2) obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were dispersed in water, and DNc , DVc was measured with a Coulter counter. When calculating DVa / DVc, a measured value of a laser scattering particle size distribution meter (LA920: manufactured by Horiba, Ltd.) was used as DVa. The volatile matter was calculated by weighing about 5 g of resin particles, drying for 45 minutes with a dryer controlled to 130 ° C., and calculating according to the following formula. The results are shown in Table 1.

Volatiles (%) = [weight of resin particles after drying / weight of resin particles before drying] × 100

  Resin particles (C-1) to (C-6) had very sharp particle size distribution. Moreover, there is little volatile matter and the solvent is removed favorably. In (RC-1), the particle size distribution deteriorated because no filtration was performed. Since (RC-2) was not treated with a screw decanter, the particle size distribution was deteriorated as in (RC-1). Moreover, since the solvent remained, volatile matter increased.

  Resin particles obtained by the production method of the present invention include paint additives, cosmetic additives, paper coating additives, slush molding resins, powder paints, electronic component manufacturing spacers, catalyst carriers, electrophotographics. It is extremely useful as toner, electrostatic recording toner, electrostatic printing toner, standard particles for electronic measuring instruments, and other resin particles for molding materials.

Claims (7)

  Dispersion medium (X0) containing liquid or supercritical carbon dioxide (X) and solvent (S) in which fine particles (A) are dispersed in a melt of resin (b) or a solvent solution of resin (b) (C1) is classified in a dispersion (X1) of resin particles (C1) in which fine particles (A) adhered to the surface of resin particles (B) containing resin (b) obtained by dispersing in And a process for producing resin particles (C) comprising fine particles (A) attached to the surfaces of the resin particles (B), the method comprising the steps of: and (X) and (S) removal.   Resin (b) precursor (b0) or a solvent solution thereof in a dispersion medium (X0) containing carbon dioxide (X) and solvent (S) in a liquid or supercritical state in which fine particles (A) are dispersed In the dispersion (X2) of the resin particles (C2) obtained by reacting (b0) with the fine particles (A) adhered to the surface of the resin particles (B) containing the resin (b). Resin particles (C) in which fine particles (A) are attached to the surface of the resin particles (B), the method comprising the steps of classifying (C2) and removing (X) and (S) Manufacturing method.   The volume average particle size DVc of the resin fine particles (C) is 1 to 20 μm, and the ratio of DVc to the number average particle size DNn of (C): DVc / DVn is 1.0 to 1.2. The manufacturing method of the resin particle (C) of description.   The production method according to claim 2 or 3, wherein the precursor (b0) of the resin (b) is a mixture of a prepolymer (α) having a reactive group and a curing agent (β).   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 4.   Resin (b) is urethane resin, epoxy resin, vinyl resin, polyester resin, polyamide resin, polyimide resin, silicon resin, fluorine resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, and polycarbonate The production method according to claim 1, which is at least one resin selected from the group consisting of resins.   Fine particles (A) are metal oxide, metal hydroxide, metal carbonate, metal sulfate, metal silicate, metal nitride, metal phosphate, metal borate, metal titanate, metal sulfide, And 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 The production method according to any one of claims 1 to 6, which is at least one selected from the group consisting of at least one organic resin fine particle (A21) and a metal salt fine particle (A23) of a long-chain fatty acid.