JP2009030000A - Method for producing nonaqueous resin dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a nonaqueous dispersion of resin particles having uniform shape and particle diameter. <P>SOLUTION: A method for producing a nonaqueous dispersion of resin particles (C) includes: dispersing a solution, prepared by dissolving a resin (b) or a precursor (bO) of the resin (b) in an organic solvent (M), in a dispersion prepared by dispersing fine particles (A) in a nonaqueous organic solvent (L), wherein when the solution of the precursor (bO) in the solvent (M) is used, the precursor (bO) is allowed to react; and forming resin particles (B) comprising the resin (b) in the dispersion of the resin particles (A) to form a nonaqueous dispersion (X) of resin particles (C) having a structure in which the fine particles (A) bond to the surfaces of the resin particles (B). <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a non-aqueous resin dispersion in which dispersed resin particles have a uniform particle size.

Non-aqueous resin dispersions are used in applications such as liquid developers for paints, electrophotography, electrostatic recording, electrostatic printing, oil-based inks for inkjet printers, inks for electronic paper, etc. From this viewpoint, it is generally required that the particle size and shape of the resin particles in the dispersion are uniform. In addition, as the resin used in the non-aqueous resin dispersion, for example, in the case of paint, polyurethane and epoxy resin are used from the viewpoint of coating strength, and in the case of electrophotographic liquid developer, from the viewpoint of constant temperature fixability. Polyester and the like are preferred. As a method for producing a non-aqueous resin dispersion using these resins, the resin is melted in advance and further dispersed by a mechanical stirring force in a nonpolar medium heated above the softening point of the resin, and then cooled. A method for obtaining a non-aqueous resin dispersion has been proposed. (For example, refer to Patent Document 1). According to this method, it is said that a non-aqueous resin dispersion having a sharp particle size distribution can be obtained even in the above resin. However, in this method, the viscosity of the resin is not sufficiently lowered and the particles are not refined, so that the obtained particle size distribution may not be sharp.
JP 09-179354 A

  An object of the present invention is to obtain a non-aqueous dispersion of resin particles having a uniform shape and particle size.

The present invention has been made in view of the above circumstances in the prior art.
That is, the resin (b) or the precursor (b0) of the resin (b) is dissolved in the organic solvent (M) in the dispersion liquid in which the fine particles (A) are dispersed in the non-aqueous organic solvent (L). In the case of using the organic solvent (M) solution of the precursor (b0), the precursor (b0) is further reacted to form the resin (b) in the dispersion of the fine particles (A). Forming a non-aqueous dispersion (X) of resin particles (C) having a structure in which fine particles (A) adhere to the surfaces of the resin particles (B). It is the manufacturing method of the non-aqueous dispersion of the resin particle (C) characterized.

The non-aqueous resin dispersion of the present invention has a uniform shape and particle size of dispersed resin particles. Furthermore, the heat resistant storage stability is good.

The present invention is described in detail below.
In the present invention, the resin (b) or the precursor (b0) of the resin (b) is contained in the organic solvent (M) in the dispersion liquid in which the fine particles (A) are dispersed in the non-aqueous organic solvent (L). When the dissolved solution is dispersed and the organic solvent (M) solution of the precursor (b0) is used, the precursor (b0) is further reacted, and the resin ( By forming the resin particles (B) comprising b), a non-aqueous dispersion (X) of resin particles (C) having a structure in which the fine particles (A) are adhered to the surfaces of the resin particles (B) is formed. This is a method for producing a non-aqueous dispersion of resin particles (C).

  The volume average particle size of the fine particles (A) is preferably 0.001 to 0.5 μm. If it is 0.001 μm or more, the surface protection effect of the resin particles (B) is increased, so that the resin particles (C) are difficult to unite, and if it is 0.5 μm or less, the particle size distribution of the resin particles (C) is small. It becomes good. Preferably it is 0.005-0.3 micrometer. 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.

  Examples of the fine particles (A) include 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.
Among these, as the fine particles (A), metal oxides such as silica, titania, zirconia, and ceria, and vinyl resins are preferable, and silica, titania, and vinyl resins are particularly preferable.

  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. The fine particles (A) are preferably well dispersed in the non-aqueous organic solvent (L), and particularly preferably hydrophobized.

  The resin particles (B) are composed of the resin (b). In the present invention, as the resin (b), a thermoplastic resin (b1), a resin (b2) obtained by finely crosslinking the thermoplastic resin, or a polymer blend containing a thermoplastic resin as a sea component and a cured resin as an island component ( Any of b3) may be sufficient. As the resin (b), two or more kinds may be used in combination. Examples of the thermoplastic resin (b1) include vinyl resins, polyurethane resins, epoxy resins, and polyester resins. Among these, a polyester resin, a mixed resin of polyester and urethane-modified polyester, a mixed resin of polyester and vinyl 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]

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

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

The number average molecular weight (measured by GPC, hereinafter abbreviated as Mn) of the resin (b) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000, and the SP value is preferably 7 to 18, more preferably. Is 8-14. Moreover, when it is desired to modify the thermal characteristics of the resin particles (C), the resin (b2) or the resin (b3) may be used. The glass transition temperature (Tg) of the resin (b) is preferably 20 ° C to 200 ° C, more preferably 40 ° C to 150 ° C. Above 20 ° C, the storage stability of the particles is good. In addition, Tg in this invention is a value calculated | required from DSC measurement.
The softening start temperature of the resin (b) is preferably 40 ° C to 220 ° C, more preferably 50 ° C to 200 ° C. Above 40 ° C, long-term storage is good. Below 220 ° C., the fixing temperature does not increase and there is no problem. In addition, the softening start temperature in this invention is a value calculated | required from a flow tester measurement.

  In the present invention, in addition to the method of using the solvent solution of the resin (b) alone, the method of using the solvent solution of the precursor (b0) of the resin (b) alone, or the above two are mixed and used. The method can be used. The solvent solution of the precursor (b0) of the resin (b) can be suitably used particularly when it is desired to introduce a crosslinking component or a high cohesive force component into the resin particles (C).

  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). Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (α) and the curing agent (β) include the following (1) and (2).
(1): The reactive group of the reactive group-containing prepolymer (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and the curing agent (β) is an active hydrogen group-containing compound (β1). There is a combination.
(2) The reactive group-containing prepolymer (α) has an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) that can react with the active hydrogen-containing group. combination.
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 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) to 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 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 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.

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.

The resin particles of the present invention can be obtained by the following production method.
A solution in which the resin (b) or the precursor (b0) of the resin (b) is dissolved in the organic solvent (M) in the dispersion obtained by dispersing the fine particles (A) in the non-aqueous organic solvent (L). When the organic solvent (M) solution of the precursor (b0) is used, the precursor (b0) is further reacted to form the resin (b) in the dispersion of fine particles (A). By forming the resin particles (B), a non-aqueous dispersion (X) of the resin particles (C) having a structure in which the fine particles (A) are adhered to the surfaces of the resin particles (B) is formed. A method for producing a non-aqueous dispersion of resin particles (C).

In the dispersion step of the above production method, the following dispersion stabilizer (D) can be used. The dispersion stabilizer (D) is a compound having at least one group of, for example, an alkyl group having 4 or more carbon atoms, a dimethylsiloxane group, and a functional group containing fluorine.
Further, it preferably has a chemical structure having an affinity for the resin (b) together with an alkyl group, a dimethylsiloxane group and a fluorine-containing group having an affinity for the non-aqueous organic solvent (L).
More specifically, among the aforementioned vinyl monomers, a monomer having an alkyl group having 4 or more carbon atoms (M1-1), a monomer having a dimethylsiloxane group (or a reactive oligomer) (M1-2), and / or Or the copolymer of the monomer (M1-3) containing a fluorine and the monomer (M2) which comprises the above-mentioned resin (b) is preferable. 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.
(CH3) 3 SiO ((CH3) 2 SiO) a Si (CH3) 2 R (where a is an average value of 15 to 45, and R is an organically modified group containing a methacryl group). Is C3 H6 OCOC (CH3) = CH2.

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- Peroxovinyl ethers such as dioxolane) (MMD) and perfluorobutenyl vinyl ether (PFBVE); vinylidene fluoride (VdF), trifluoroethylene, 1,2-difluoroethylene, vinyl fluoride, trifluoropropylene, 3, 3, 3-trifluoro-2-to Hydrogen atom-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.
Reamine (16), polythiol (17) and the like are preferable.

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) is preferably dissolved in the non-aqueous organic solvent (L).
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 for dispersing the resin fine particles (A) in the non-aqueous organic solvent (L). For example, (A) and (L) are charged in a container, and stirring, spraying, ultrasonic irradiation is performed. For example, a method of directly dispersing (A) in (L), a method of introducing the solvent dispersion of (A) into (L), and the like. The fine particles (A) are preferably those that do not dissolve in (L) and are stably dispersed in (L).

The non-aqueous organic solvent (L) used in the present invention is preferably an organic solvent in which the solubility of the resin (b) is 1% by weight or less. If the solubility of the resin (b) is 1% by weight or less, it is preferable that the resin particles (C) are difficult to unite with each other. The solubility of the resin (b) in the non-aqueous organic solvent (L) is the mass of the supernatant obtained by sedimentation of the resin particles in the non-aqueous dispersion (X) by centrifugation, and the organic solvent ( The value obtained by dividing the mass of the residue after drying at the boiling point of L).
Specifically, it is calculated by the following procedure.
The non-aqueous dispersion (X) is centrifuged at 3000 rpm for 10 minutes, and about 2 g (wg) of the supernatant is collected in an aluminum container. Further, the supernatant is dried for 1 hour in a vacuum dryer under the temperature condition of the boiling point of the organic solvent (L), and the mass of the residue is weighed. If the residue mass at this time is Wg, the solubility of the resin (b) in the non-aqueous organic solvent (L) can be calculated by W / w × 100 [%].

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

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

For example, when polyester, polyurethane, or epoxy resin is selected as the resin (b), preferable organic solvents (M) include acetone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and a mixed solvent of two or more of these. Can do.
The method for dissolving the resin (b) or the precursor (b0) of the resin (b) in the organic solvent (M) may be any method, and a known method can be used, for example, in the organic solvent (M). Examples thereof include a method in which the resin (b) or the precursor (b0) is charged and stirred, and a method in which heating is performed.

The solvent solution of the resin (b) or the solvent (M) of the resin (b) is preferably moderate viscosity because it is dispersed in (L), and preferably 100 Pa · s or less from the viewpoint of particle size distribution. The pressure is preferably 10 Pa · s or less. The solubility of the resin (b) in (L) 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 solvent solution of the resin (b) of the present invention, the solvent solution of the precursor (b0) of the resin (b), and a mixture thereof, other additives (colorant, release agent, charge control agent, oxidation agent) An inhibitor, an antiblocking agent, a heat stabilizer, a fluidizing agent, and the like).

Known dyes, pigments and magnetic powders can be used as the colorant (E). Specifically, carbon black, Sudan Black SM, First Yellow-G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Examples include rhodamine FB, rhodamine B lake, methyl violet B lake, phthalocyanine blue, pigment blue, prilliant green, phthalocyanine green, oil yellow GG, kayaset YG, orazol brown B, oil pink OP, magnetite, iron black and the like.
The amount of colorant used is usually based on the weight of the resin (b) when a dye or pigment is used.

  Examples of the charge control agent include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts). ), Alkylamide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, metal salt of salicylic acid derivative, and the like. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinaclide And azo pigments, and other high molecular compounds having a functional group such as a sulfo group, a carboxyl group, and a quaternary ammonium salt. The usage-amount of a charge control agent is 0-5 weight% normally based on the weight of resin (b).

As a method of mixing other additives in the resin (b), the solvent solution of the resin (b), the solvent solution of the precursor (b0) of the resin (b), and these additives are mixed in advance. After that, it is preferable to add and disperse the mixture in (L). A known method can be applied to the solvent solution of the resin (b), the solvent solution of the precursor (b0) of the resin (b), and the method of mixing the additive into these mixtures. And a mixing method using a pulverizer, a kneader or the like.

In the present invention, any method may be used for dispersing the resin (b) or the solvent solution of the resin (b) in the non-aqueous organic solvent (L) in which the fine particles (A) are dispersed.
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 through a spray nozzle into (L) to form droplets, Examples thereof include a method in which the resin in the droplet is supersaturated and the resin particles are precipitated, and a method in which ultrasonic waves are irradiated.
Thus, by dispersing the resin (b) in (L) and allowing the resin fine particles (A) to be adsorbed on the surface and growing the dispersed resin (b), the surface of the resin particles (B) Resin particles (C1) having fine particles (A) fixed thereto are formed. A dispersion in which (C1) is dispersed in (L) is referred to as dispersion (X).

In the production method of the present invention, the operations performed in the non-aqueous organic solvent (L) are fine particles (A), resin particles (B), resin particles (C), non-aqueous organic solvent (L), and organic solvent (M). It is preferable to carry out within a temperature range in which no thermal deterioration occurs, and specifically 200 ° C. or less is preferred. 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.
In the present invention, the organic solvent (M) contained in the non-aqueous dispersion (X) is preferably removed, and a known desolvation method can be applied as the removal method. A method of heating, a method of heating, a method of bubbling air or nitrogen.

The volume average particle diameter of the resin particles (B) is preferably 0.1 to 10 μm, more preferably 0.2 to 8 μm. The ratio of the volume average particle diameter of the resin fine particles (A) to the volume average particle diameter of the resin particles (C) is preferably 0.0001 to 0.2, more preferably 0.0005 to 0.1.
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 0.3, more preferably 0.002 to 0.2, More preferably, it is 0.003-0.1, Most preferably, it is 0.01-0.08. 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 resin particles (C) is preferably 0.1 to 10 μm, more preferably 0.2 to 8 μm, still more preferably 0.3 to 6 μm.
The ratio DVc / DNc of the volume average particle diameter DVc of (C) and the number average particle diameter DNc of (C) is preferably 1.0 to 1.5, more preferably 1.0 to 1.4, and still more preferably. 1.0 to 1.3.
The volume average particle diameter of the resin particles (C) can be adjusted by the addition amount of the fine particles (A).
If the addition amount of the fine particles (A) is increased, the volume average particle diameter of the resin particles (C) is decreased.

From the viewpoint of particle size uniformity, 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 fine particles (A), and the surface of (B) More preferably, 30% or more of 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

The non-aqueous dispersion obtained from the production method of the present invention is particularly useful as a liquid developer. In this case, the non-aqueous dispersion is used as a liquid developer for electrophotography, electrostatic recording, and electrostatic printing. used.
As a method for producing the liquid developer, in the method for producing a non-aqueous dispersion, the dielectric constant of the non-aqueous organic solvent (L) is 1 to 4, and the solvent solution or resin (b) of the resin (b) The colorant (E) is further added to the solvent solution of the precursor (b0).
In this case, examples of the non-aqueous organic solvent (L) include octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isopar E, isopar. G, Isopar H, Isopar L (isopar: trade name of Exxon), Shellsol 70, Shellsol 71 (shellsol: trade name of Shell Oil), Amsco OMS, Amsco 460 (Commercial name of Amsco: Spirits) Silicone oil or the like can be used alone or in combination.
As the colorant (E), the above-mentioned colorant (E) can be appropriately used. Moreover, in order to control the charging property, the above-described charge adjusting agent may be used.

  The non-aqueous dispersion of the present invention has a uniform particle size and shape. Therefore, the non-aqueous dispersion of the present invention is useful as a liquid developer for paints, electrophotography, electrostatic recording, electrostatic printing and the like, oil-based ink for inkjet printers, and ink for electronic paper. As other applications, it is also useful for cosmetics, spacers for manufacturing electronic components, and electrorheological fluids.

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 Fine Particle (A-1) Dispersion>
In a vessel equipped with a stirrer and a temperature controller, 900 parts of silica-ethyl acetate dispersion (EAC-ST, manufactured by Nissan Chemical Industries) and 100 parts of hexamethyldisilazane are added and reacted at 60 ° C. for 1 hour. After adding 810 parts of normal decane, ethyl acetate was removed with an evaporator to obtain [silica fine particle (A-1) dispersion]. The solid content concentration was 9%.

Production Example 2 <Preparation of resin fine particle (A-2) dispersion>
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a dropping funnel, and a nitrogen blowing tube, 871 parts of normal hexane was charged, and 42 parts of normal decane and behenyl acrylate (22 carbon atoms) were placed in another glass beaker. Acrylate of an alcohol having a linear alkyl group) 52 parts, 0.3 part of azobismethoxydimethylvaleronitrile, 35 parts of methacryl-modified silicone (X-22-2426, manufactured by Shin-Etsu Chemical Co., Ltd.), and stirring at 20 ° C., A monomer solution was prepared by mixing, and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 40 ° C. for 1 hour in a sealed state. 3 hours after the completion of dropping, a mixture of 0.3 part of azobismethoxydimethylvaleronitrile and 42 parts of normal hexane was added to a separate container, aged at 40 ° C. for 3 hours, cooled to room temperature, and resin fine particles (A-2) A dispersion was obtained.

Production Example 3 <Preparation of Metal Soap Fine Particle (A-3) Dispersion>
In an autoclave equipped with a stirrer, 700 parts of normal decane, 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 (CH2) 3 (CH3)} 2SiO ((CH3) 2 SiO) nSi (CH3) 2 (CH2) 3COOH ( functional group equivalent: 2,000)

Production Example 4 <Preparation of Resin (b-1)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 831 parts of propylene glycol, 703 parts of terephthalic acid, 47 parts of adipic acid, and 0.5 part of tetrabutoxytitanate as a condensation catalyst were placed at 180 ° C. with nitrogen. The reaction was carried out for 8 hours while distilling off the methanol produced under an air stream. Next, while gradually raising the temperature to 230 ° C., the reaction is performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction is performed under a reduced pressure of 0.01 to 0.03 MPa. When it reached 87 ° C., it was cooled to 180 ° C., 24 parts of trimellitic anhydride and 0.5 part of tetrabutoxy titanate were added, reacted for 90 minutes, and then taken out. The recovered propylene glycol was 442 parts. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a resin (b-1). Resin (b-1) had Mn of 1900 and a glass transition temperature of 45 ° C. Resin (b-1) was soluble in acetone and toluene and insoluble in ethanol.

Production Example 5 <Preparation of Resin (b-2)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 729 parts of propylene glycol, 683569 parts of terephthalic acid, 67 parts of adipic acid, 38 parts of trimellitic anhydride and 0.5 part of tetrabutoxy titanate as a condensation catalyst. The mixture was allowed to react at 180 ° C. for 8 hours while distilling off the produced methanol under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and the reaction was further performed under a reduced pressure of 0.01 to 0.03 MPa. The recovered propylene glycol was 172 parts. It was taken out when the softening point reached 160 ° C., cooled to room temperature, pulverized and granulated to obtain a resin (b-2). Resin (b-2) had Mn of 5700 and a glass transition temperature of 63 ° C. Resin (b-1) was soluble in acetone and toluene and insoluble in ethanol.

Production Example 6 <Preparation of Prepolymer (b0-1) Solution>
In a reaction vessel equipped with a stirrer and a dehydrator, 681 parts of bisphenol A / EO 2 mol adduct, 81 parts of bisphenol A / PO 2 mol adduct, 275 parts of terephthalic acid, 7 parts of adipic acid, 22 parts of trimellitic anhydride, dibutyl After adding 2 parts of tin oxide and performing a dehydration reaction at 230 ° C. under normal pressure for 5 hours, a dehydration reaction was performed under a reduced pressure of 0.01 to 0.03 MPa for 5 hours to obtain a polyester. This polyester had 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, 50 parts of isophorone diisocyanate, and 600 parts of MEK were put into an autoclave, and reacted in a sealed state at 100 ° C. for 5 hours to obtain a prepolymer (b0-1) solution having an isocyanate group at the molecular end. The NCO content of the prepolymer (b0-1) solution was 1.5%. The solid content concentration was 45%.

Production Example 7 <Production of ketimine compound (b0-2)>
Hexamethylenediamine and excess methyl ethyl ketone (4 times molar amount with respect to the diamine) were refluxed at 80 ° C. for 24 hours, and the generated water was removed from the system. Thereafter, unreacted methyl ethyl ketone was removed under reduced pressure to obtain a ketimine compound (B-1). (B-1) has a total amine value of 414 and a valence of 2.

Production Example 8 <Production of Wax Dispersion>
In an autoclave equipped with an ultrasonic irradiator and temperature controller, 300 parts of olefin wax (melting point 80 ° C.) and 700 parts of DMF are charged, heated to 90 ° C., and then irradiated with ultrasonic waves at 20 KHz and 600 W while cooling. Thus, wax fine particles were precipitated to obtain a wax dispersion (W-1).

Production Example 9 <Production of pigment dispersion>
240 parts of carbon black, 700 parts of DMF, and 60 parts of a pigment dispersant (Solsperse 28000, manufactured by Avicia) are mixed, and pulverized using zirconia beads having a particle diameter of 0.3 mm in a bead mill (Dynomill Multilab: manufactured by Shinmaru Enterprises). To obtain a pigment dispersion (P-1).

Production Example 10 <Preparation of Resin Solution (bs-1)>
In a container equipped with a stirrer, 700 parts of DMF and 300 parts of the resin (b-1) obtained in Production Example 1 were charged and stirred until completely dissolved to obtain a resin solution (bs-1).

Production Example 11 <Preparation of Resin Solution (bs-2)>
In a container equipped with a stirrer, 700 parts of DMF and 300 parts of the resin (b-2) obtained in Production Example 2 were charged and stirred until completely dissolved to obtain a resin solution (bs-2).

Production Example 12 <Preparation of Resin (b-3)>
Into an autoclave reaction vessel equipped with a thermometer and a stirrer, 646 parts of xylene were placed, and after substitution with nitrogen, 746 parts of styrene, 140 parts of acrylonitrile, 154 parts of stearyl methacrylate, 15.5 parts of di-t-butyl peroxide and 118 of xylene Part of the mixed solution was added dropwise at 170 ° C. over 3 hours, and the temperature was further maintained at this temperature for 30 minutes. Next, the solvent was removed to obtain a resin (b-3). The weight average molecular weight of the resin (b-3) was 10,000 and Tg 60 ° C.

Production Example 13 <Preparation of Resin Solution (bs-3)>
In a container equipped with a stirrer, 700 parts of DMF and 300 parts of the resin (b-3) obtained in Production Example 12 were charged and stirred until completely dissolved to obtain a resin solution (bs-3).

Example 1
The raw materials were charged into the beaker at the following mass ratio, and stirred and mixed with a spatula to obtain a raw material dispersion (Y-1).
Resin solution (bs-1) 340 parts Resin solution (bs-2) 85 parts Wax dispersion (W-1) 50 parts Pigment dispersion (P-1) 25 parts Next, 292 parts of normal decane in another beaker Then, 208 parts of the silica fine particle (A-1) dispersion liquid was added, and after mixing for 10 seconds at a rotation speed of 8000 rpm with a homomixer (manufactured by Primics), the raw material dispersion liquid (Y-1) was charged all at once with stirring. An aqueous dispersion (X0-1) was obtained by dispersing for 1 minute. Furthermore, DMF in the system was removed by removing (X0-1) with an evaporator at 40 ° C. and 0.01 MPa to obtain a non-aqueous dispersion (X-1).

Example 2
The raw materials were charged into the beaker at the following mass ratio, and stirred and mixed with a spatula to obtain a raw material dispersion (Y-2).
Resin solution (bs-1) 328 parts Prepolymer solution (b0-1) 55 parts Ketimine compound (b0-2) 5 parts Wax dispersion (W-1) 51 parts Pigment dispersion (P-1) 26 parts Next Into another beaker, 310 parts of normal decane and 203 parts of silica fine particle (A-1) dispersion were added and mixed with a homomixer (manufactured by Primics) at a rotation speed of 8000 rpm for 10 seconds. (Y-2) was added all at once, 14 parts of an aqueous THF solution was further added, and then dispersed for 1 minute to obtain an aqueous dispersion (X0-2). Further, (X0-2) was removed with an evaporator at 40 ° C. and 0.01 MPa to remove DMF, THF, water, and MEK in the system to obtain a non-aqueous dispersion (X-2).

Example 3
In Example 1, a non-aqueous dispersion (X-3) was obtained in the same manner as in Example 1 except that the following charging ratio was used.
Resin solution (bs-1) 340 parts Resin solution (bs-3) 85 parts Wax dispersion (W-1) 50 parts Pigment dispersion (P-1) 25 parts

Example 4
In Example 1, in place of 292 parts of normal decane and 208 parts of the silica fine particle (A-1) dispersion liquid, 563 parts of the fine particle (A-2) dispersion liquid were used. A liquid (X-4) was obtained.

Example 5
In Example 1, non-aqueous dispersion was performed in the same manner as in Example 1, except that 292 parts of normal decane and 208 parts of the silica fine particle (A-1) dispersion liquid were replaced with 500 parts of the fine particle (A-3) dispersion liquid. A liquid (X-5) was obtained.

Example 6
In Example 1, a non-aqueous dispersion (X-6) was obtained in the same manner as in Example 1 except that silicone oil (polydimethylsiloxane, molecular weight 1,000) was used instead of normal decane.

Production Example 14 <Preparation of Resin Solution (bs-4)>
In Production Example 10, a resin solution (bs-4) was obtained in the same manner as in Production Example 10, except that acetone was used instead of dimethylformamide.

Production Example 15 <Preparation of Resin Solution (bs-5)>
In Production Example 11, a resin solution (bs-5) was obtained in the same manner as in Production Example 11 except that acetone was used instead of dimethylformamide.

Production Example 16 <Production of Wax Dispersion>
In Production Example 8, a wax dispersion (W-2) was obtained in the same manner as in Production Example 8, except that acetone was used instead of dimethylformamide.

Production Example 17 <Production of Pigment Dispersion>
In Production Example 9, a pigment dispersion (P-2) was obtained in the same manner as in Production Example 9, except that acetone was used instead of dimethylformamide.

Example 7
In Example 1, the resin solution (bs-4) is used instead of the resin solution (bs-1), the resin solution (bs-5) is used instead of the resin solution (bs-2), and the wax dispersion (W-1) is used. Example), except that the wax dispersion (W-2) was used instead of the pigment dispersion (P-1) instead of the pigment dispersion (P-1), and the following raw material charge ratios were used. As in 1, a non-aqueous dispersion (X-7) was obtained.
Resin solution (bs-4) 340 parts Resin solution (bs-5) 85 parts Wax dispersion (W-2) 50 parts Pigment dispersion (P-2) 25 parts

Comparative Example 1
In Example 1, in place of 292 parts of normal decane and 208 parts of the dispersion of silica fine particles (A-1), 500 parts of normal decane was used instead of the non-aqueous dispersion (X-8 ′). )

Measurement Examples of Physical Properties Volume average particle diameters (DVc) and number average particle diameters of non-aqueous dispersions (X-1) to (X-7) and (X-8 ′) obtained in Examples 1 to 7 and Comparative Example 1 (DNc) was measured with a dynamic light scattering particle size distribution analyzer (LB-550: manufactured by Horiba, Ltd.).

Moreover, the heat resistant storage stability of the non-aqueous dispersion was evaluated by the following method. That is, after allowing the non-aqueous dispersion to stand for 24 hours in a dryer controlled to 50 ° C., the particle size distribution was measured, and the following criteria were evaluated by the change in the particle size distribution before and after heating.
○: The particle size distribution does not change and is not blocked.
Δ: The particle size distribution changes, but it returns to the original particle size distribution by ultrasonic dispersion (20 kHz, 200 W, 1 minute).
×: The particle size distribution has changed, and the original particle size distribution is not restored even when ultrasonic dispersion is performed.

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

(C-1) to (C-7) have a small volume average particle size / number average particle size and a sharp particle size distribution, whereas (C-8 ′) has a large particle size, and The particle size distribution was significantly deteriorated. Further, the heat resistant storage stability was good in (C-1) to (C-7), whereas (C-8 ') was deteriorated.

  The non-aqueous dispersion of the present invention has a uniform particle size and shape of dispersed particles. Therefore, the non-aqueous dispersion of the present invention is useful as a liquid developer for paints, electrophotography, electrostatic recording, electrostatic printing and the like, oil-based ink for inkjet printers, and ink for electronic paper. As other applications, it is also useful for cosmetics, spacers for manufacturing electronic components, and electrorheological fluids.

Claims (9)

A solution in which the resin (b) or the precursor (b0) of the resin (b) is dissolved in the organic solvent (M) in the dispersion obtained by dispersing the fine particles (A) in the non-aqueous organic solvent (L). When the organic solvent (M) solution of the precursor (b0) is used, the precursor (b0) is further reacted to form the resin (b) in the dispersion of fine particles (A). By forming the resin particles (B), a non-aqueous dispersion (X) of the resin particles (C) having a structure in which the fine particles (A) are adhered to the surfaces of the resin particles (B) is formed. A method for producing a non-aqueous dispersion of resin particles (C). The process according to claim 1, wherein the solubility of the resin (b) in the non-aqueous organic solvent (L) is 1% by weight or less. The production method according to claim 1 or 2, wherein the organic solvent (M) is further removed from the non-aqueous dispersion of the resin particles (C). The production method according to any one of claims 1 to 3, wherein the volume average particle size of the fine particles (A) is 0.001 to 0.5 µm. The manufacturing method according to any one of claims 1 to 4, wherein the fine particles (A) are metal oxide fine particles, and the surface of the fine particles (A) is subjected to a hydrophobic treatment. The production method according to any one of claims 1 to 4, wherein the fine particles (A) are vinyl resin fine particles. The production method according to any one of claims 1 to 4, wherein the fine particles (A) are metal soap fine particles. The solubility parameter of an organic solvent (M) is 9.5-20, The manufacturing method of any one of Claims 1-7. The manufacturing method according to any one of claims 1 to 8, wherein the dielectric constant of the non-aqueous organic solvent (L) is 1 to 4, and the resin (b) or resin in the organic solvent (M). A method for producing a liquid developer, wherein the colorant (E) is further added to a solution in which the precursor (b0) of (b) is dissolved.