JP2013155210A - Core-shell type resin particle, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a core-shell type resin particle excellent in pressure fixability and heat-resistive preservability.SOLUTION: A method for manufacturing a resin particle (C) includes mixing a dispersion (Y) and an oily liquid (G) to obtain a composite dispersion (Z), and thereafter solidifying (Z), wherein the dispersion (Y) is a dispersion in which a resin (b), a solvent solution of the resin (b), a precursor (b0) of the resin (b) or a solvent solution of (b0) is dispersed in a nonaqueous medium (X); and the oily liquid (G) is a melted one of a resin (a), a solvent solution of the resin (a), a precursor (a0) of the resin (a) or a solvent solution of (a0); and the resin particle (C) is a resin particle in which the resin (a) is adhered on the surface of a resin particle (B) containing the resin (b).

Description

  The present invention relates to core-shell type resin particles and a method for producing the same. More specifically, the present invention relates to a core-shell type resin particle useful as an intermediate for electrophotographic toner, electrostatic recording toner, electrostatic printing toner, and the like.

Conventionally, a technology for fixing toner with low energy has been desired, and development of a toner capable of fixing at a lower temperature has been underway.
As a means for lowering the toner fixing temperature, it is common practice to lower the melt viscosity of the resin. However, when it is used as a toner for electrophotography, there is a limit to lowering the viscosity of the resin because heat-resistant storage stability that requires storage in a container during transportation and in a toner cartridge is required. In order to solve this problem, there has been proposed a microcapsule toner which contains a binder resin solution in a core material and is covered with an outer shell and can be fixed only by pressure (Patent Document 1).
However, a strong outer shell is required to ensure storage stability, and a pressure device of 20 MPa is necessary for fixing only by pressure, which is not practical.

JP-A-8-30018

  The present invention has been made in view of the above problems, and an object of the present invention is to provide core-shell type resin particles that are excellent in pressure fixability and heat-resistant storage stability.

As a result of intensive studies to achieve the above object, the present inventors have reached the present invention.
That is, the present invention is characterized in that the dispersion (Y) and the oily liquid (G) are mixed to obtain a composite dispersion (Z), and then (Z) is solidified to obtain resin particles (C). The dispersion (Y) is a resin (b), a solvent solution of the resin (b), a precursor of the resin (b) (b0) or a solvent of (b0). A dispersion obtained by dispersing a solution in a non-aqueous medium (X), in which an oily liquid (G) is obtained by melting the resin (a), a solvent solution of the resin (a), and a precursor of the resin (a) (A0) or a solvent solution of (a0), and the resin particles (C) are resin particles obtained by adhering the resin (a) to the surface of the resin particles (B) containing the resin (b). It is a manufacturing method of a certain resin particle (C).

  The core-shell type resin particles of the present invention obtained by the production method of the present invention are excellent in pressure fixability and heat resistant storage stability.

The dispersion (Y) in the present invention includes [1] a resin (b) dispersed in a non-aqueous medium (X), [2] a solvent solution of the resin (b) in the non-aqueous medium (X). [3] a resin (b) precursor (b0) dispersed in a non-aqueous medium (X), or [4] a solvent solution of (b0) in a non-aqueous medium ( X) dispersed in.
The resin (b) in the present invention may be a thermoplastic resin or a thermosetting resin. For example, vinyl resin, polyester resin, polyurethane resin, epoxy resin, polyamide resin, polyimide resin, silicon resin, Examples thereof include phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, and polycarbonate resin. In addition, 2 or more types of the said resin may be used together for resin (b).
Among these, a vinyl resin, a polyester resin, a polyurethane resin, an epoxy resin, and a combination thereof are preferable from the viewpoint that resin particles (B) having a small particle diameter are easily obtained.

  The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a monomer having a polymerizable double bond. Examples of the monomer having a polymerizable double bond include the following (1) to (9).

(1) Hydrocarbon having a polymerizable double bond:
(1-1) Aliphatic hydrocarbon having a polymerizable double bond:
(1-1-1) Chain hydrocarbon having a polymerizable double bond: Alkene having 2 to 30 carbon atoms (for example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.) An alkadiene having 4 to 30 carbon atoms (for example, butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, etc.);
(1-1-2) Cyclic hydrocarbon having a polymerizable double bond: mono or dicycloalkene having 6 to 30 carbon atoms (for example, cyclohexene, vinylcyclohexene, ethylidenebicycloheptene, etc.) and monocyclic having 5 to 30 carbon atoms Or dicycloalkadiene [for example, (di) cyclopentadiene etc.] etc.
(1-2) Aromatic hydrocarbon having a polymerizable double bond: styrene; hydrocarbyl (alkyl having 1 to 30 carbon atoms, cycloalkyl, aralkyl and / or alkenyl) substituted styrene (for example, α-methylstyrene) Vinyl toluene, 2,4-dimethylstyrene, ethyl styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, and trivinyl benzene); and vinyl Naphthalene etc.

(2) Monomers having a carboxyl group and a polymerizable double bond and their salts:
C3-C15 unsaturated monocarboxylic acid {For example, (meth) acrylic acid ["(meth) acryl" means acryl or methacryl. ], Crotonic acid, isocrotonic acid, cinnamic acid and the like}; C3-C30 unsaturated dicarboxylic acid (anhydride) [for example, (anhydrous) maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid, mesaconic acid, etc. And monoalkyl (C1-10) esters of unsaturated dicarboxylic acids having 3 to 10 carbon atoms (eg maleic acid monomethyl ester, maleic acid monodecyl ester, fumaric acid monoethyl ester, itaconic acid monobutyl ester and citracone) Acid monodecyl ester, etc.).
Examples of the salt constituting the monomer salt having a carboxyl group and a polymerizable double bond include alkali metal salts (such as sodium salt and potassium salt), alkaline earth metal salts (such as calcium salt and magnesium salt), and ammonium. Examples thereof include salts, amine salts, and quaternary ammonium salts.
The amine salt is not particularly limited as long as it is an amine compound. For example, primary amine salts (such as ethylamine salts, butylamine salts and octylamine salts), secondary amines (such as diethylamine salts and dibutylamine salts), tertiary amines ( Triethylamine salt and tributylamine salt). Examples of the quaternary ammonium salt include tetraethylammonium salt, triethyllaurylammonium salt, tetrabutylammonium salt, and tributyllaurylammonium salt.
Examples of the salt of the monomer having a carboxyl group and a polymerizable double bond include sodium acrylate, sodium methacrylate, monosodium maleate, disodium maleate, potassium acrylate, potassium methacrylate, monopotassium maleate, acrylic Examples include lithium acid, cesium acrylate, ammonium acrylate, calcium acrylate, and aluminum acrylate.

(3) Monomers having a sulfo group and a polymerizable double bond and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms (for example, vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid); styrene sulfonic acid and alkyl (2 to 24 carbon) derivatives thereof (for example, α-methyl styrene sulfone) Acid etc .; C5-C18 sulfo (hydroxy) alkyl- (meth) acrylate (for example, sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloyloxy) Ethanesulfonic acid and 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid); sulfo (hydroxy) alkyl (meth) acrylamide having 5 to 18 carbon atoms [eg 2- (meth) acryloylamino-2,2- Dimethylethanesulfonic acid, 2- (meth) acrylic Do-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, etc.]; alkyl (C3-C18) allylsulfosuccinic acid (for example, propylallylsulfosuccinic acid, butylallylsulfosuccinic acid, 2- Ethylhexyl-allylsulfosuccinic acid, etc.); poly [n (degree of polymerization, the same applies hereinafter) = 2-30] oxyalkylene (oxyethylene, oxypropylene, oxybutylene, etc.). Oxyalkylene may be used alone or in combination. The addition type may be random addition or block addition.) Sulfate ester of mono (meth) acrylate [for example, poly (n = 5-15) oxyethylene monomethacrylate sulfate and poly (n = 5-15) oxypropylene monomethacrylate sulfate Esters etc.]; Compounds represented by the general formulas (1) to (3); and salts thereof.
In addition, as a salt, what was illustrated as a salt which comprises the salt of the monomer which has (2) a carboxyl group and a polymerizable double bond is mentioned.

O— (R ¹ O) _m SO ₃ H
｜
_{CH 2 = CHCH 2 OCH 2 CHCH} 2 O-Ar-R 2 (1)



CH = CH-CH ₃
｜
R ³ —Ar—O— (R ¹ O) _n SO ₃ H (2)

CH ₂ COOR ⁴
｜
HOSO ₂ CHCOOCH ₂ CH (OH) CH ₂ OCH ₂ CH═CH ₂ (3)

In the formula, R ¹ is an alkylene group having 2 to 4 carbon atoms, and R ¹ O may be used alone or in combination of two or more, and when two or more are used in combination, the bonding form may be random or block. R ² and R ³ are each independently an alkyl group having 1 to 15 carbon atoms; m and n are each independently a number of 1 to 50; Ar is a benzene ring; R ⁴ is substituted with a fluorine atom; Or an alkyl group having 1 to 15 carbon atoms.

(4) Monomers and salts thereof having a phosphono group and a polymerizable double bond:
(Meth) acryloyloxyalkyl phosphate monoester (alkyl group having 1 to 24 carbon atoms) (for example, 2-hydroxyethyl (meth) acryloyl phosphate and phenyl-2-acryloyloxyethyl phosphate), (meth) acryloyloxyalkyl Phosphonic acid (alkyl group having 1 to 24 carbon atoms) (for example, 2-acryloyloxyethylphosphonic acid).
In addition, as a salt, what was illustrated as a salt which comprises the monomer which has (2) a carboxyl group and a polymerizable double bond is mentioned.

(5) Monomer having a hydroxyl group and a polymerizable double bond:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(6) Nitrogen-containing monomer having a polymerizable double bond:
(6-1) Monomer having amino group and polymerizable double bond:
Aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole Aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof.
(6-2) Monomer having amide group and polymerizable double bond:
(Meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide, N, N -Dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like.
(6-3) A monomer having 3 to 10 carbon atoms having a nitrile group and a polymerizable double bond:
(Meth) acrylonitrile, cyanostyrene, cyanoacrylate and the like.
(6-4) Monomers having 8 to 12 carbon atoms having a nitro group and a polymerizable double bond:
Nitrostyrene etc.

(7) Monomer having 6 to 18 carbon atoms having an epoxy group and a polymerizable double bond:
Glycidyl (meth) acrylate and the like.

(8) C2-C16 monomer having a halogen element and a polymerizable double bond:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(9) An ester having a polymerizable double bond, an ether having a polymerizable double bond, a ketone having a polymerizable double bond, and a sulfur-containing compound having a polymerizable double bond:
(9-1) C4-C16 ester having a polymerizable double bond:
Vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl -Α-ethoxyacrylate, 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 and eicosyl (meth) a Relate, etc.], dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two alkyl groups are carbon atoms 2-8 linear, branched or alicyclic groups), poly (meth) allyloxyalkanes (diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetra Monomers having a polyalkylene glycol chain and a polymerizable double bond, such as allyloxybutane and tetrametaallyloxyethane) [polyethylene glycol [number average molecular weight (hereinafter abbreviated as Mn) = 300] mono (meth) acrylate , Polypropylene glycol (Mn = 500) monoacrylate, methyl alcohol ethylene oxide (hereinafter ethylene oxide is abbreviated as EO) 10 mol adduct (meth) acrylate and lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like].
(9-2) C3-C16 ether having a polymerizable double bond:
Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4-dihydro -1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, acetoxystyrene, phenoxystyrene, and the like.
(9-3) C4-C12 ketone having a polymerizable double bond:
Examples include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.
(9-4) Sulfur-containing compound having 2 to 16 carbon atoms having a polymerizable double bond:
Examples thereof include divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, and divinyl sulfoxide.

  Specific examples of the vinyl resin include styrene- (meth) acrylic acid ester copolymer, styrene-butadiene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-acrylonitrile copolymer, Styrene- (maleic anhydride) copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid-divinylbenzene copolymer and styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer Examples include coalescence.

As the polyester resin, a polycondensate of a polyol and a polycarboxylic acid, an acid anhydride thereof, or a lower alkyl (alkyl group having 1 to 4 carbon atoms) can be used. A known polycondensation catalyst or the like can be used for the polycondensation reaction.
Examples of the polyol include a diol (10) and a trivalent to octavalent or higher polyol (11).
As the polycarboxylic acid, its acid anhydride or lower alkyl ester, dicarboxylic acid (12), tri- or hexavalent or higher polycarboxylic acid (13), these acid anhydrides and lower alkyl esters are used.
The ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/5, more preferably 1.5 / 1 to 1 as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1/4, particularly preferably 1.3 / 1 to 1/3.

Examples of the diol (10) include alkylene glycols having 2 to 30 carbon atoms (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol). , Decanediol, dodecanediol, tetradecanediol, neopentylglycol, 2,2-diethyl-1,3-propanediol, etc.); Mn = 106-10,000 alkylene ether glycol (for example, diethylene glycol, triethylene glycol, dipropylene) Glycols, polyethylene glycols, polypropylene glycols and polytetramethylene ether glycols); alicyclic diols having 6 to 24 carbon atoms (for example, 1,4-cyclohexanedimethanol and hydrogenated bisphenol) Knoll A, etc.); Mn = 100-10,000 alkylene oxide (hereinafter abbreviated as AO) adduct (addition mole number 2-100) (for example, 1,4-cyclohexanedimethanol EO 10 mol) Adducts, etc.]; AO [EO, propylene oxide (hereinafter referred to as bisphenols having 15 to 30 carbon atoms, such as bisphenol A, bisphenol F and bisphenol S) or polyphenols having 12 to 24 carbon atoms (such as catechol, hydroquinone and resorcinol) Abbreviated to PO) and butylene oxide, etc.] adducts (addition mole number 2-100) (for example, bisphenol A · EO 2-4 mol adduct and bisphenol A · PO 2-4 mol adduct, etc.); weight average molecular weight (hereinafter Mw) Abbreviation) = 100-5,000 polylactonedio Le (e.g. poly -ε- caprolactone diol); polybutadiene diol Mw = 1,000 to 20,000, and the like.
Of these, an AO adduct of alkylene glycol and bisphenols is preferred, and an AO adduct of bisphenols and a mixture of an AO adduct of bisphenols and alkylene glycol are more preferred.

Examples of the trivalent to octavalent or higher polyol (11) include trivalent to octavalent or higher aliphatic polyhydric alcohols having 3 to 10 carbon atoms (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan). And AO (2 to 4 carbon atoms) adduct (addition mole number 2 to 100) of trisphenol having 25 to 50 carbon atoms (for example, trisphenol · EO 2 to 4 mol adduct and trisphenol PA · PO 2 −). 4 mol adducts, etc.); AO (carbon number 2-4) adducts (addition mol number 2-100) (phenol novolac PO 2 mol adducts) of 3 to 50 novolak resins (for example, phenol novolak and cresol novolak). And phenol novolac EO 4 mol adduct); polyphenols having 6 to 30 carbon atoms (examples) Pyrogallol, phloroglucinol, 1,2,4-benzenetriol and the like) AO (carbon number 2 to 4) adduct (addition mole number 2 to 100) (pyrogallol EO 4 mol adduct); and polymerization degree 20 to 2 , 1,000 acrylic polyol {copolymer of hydroxyethyl (meth) acrylate and other polymerizable double bond monomer [for example, styrene, (meth) acrylic acid, (meth) acrylic acid ester, etc.]} Etc.
Of these, an AO adduct of an aliphatic polyhydric alcohol and a novolac resin is preferred, and an AO adduct of a novolak resin is more preferred.

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

Examples of the polyurethane resin include polyisocyanate (14) and active hydrogen-containing compound {water, polyol [the diol (10) (including diol having a functional group other than hydroxyl group), and 3 to 8 or more polyols ( 11)], polycarboxylic acid [dicarboxylic acid (12) and polycarboxylic acid (13) having a valence of 3 to 6 or more], polyester polyol obtained by polycondensation of polyol and polycarboxylic acid, and C6-12. A ring-opening polymer of lactone, a polyamine (15), a polythiol (16), and a polyaddition product of these, etc.} , Primary and / or secondary monoamines in equal amounts relative to the isocyanate groups of the prepolymer ( 7) and reacting the obtained, and amino group-containing polyurethane resins.
The content of carboxyl groups in the polyurethane resin is preferably 0.1 to 10% by weight.

  As the polyisocyanate (14), an aromatic polyisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter), an aliphatic polyisocyanate having 2 to 18 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, etc.) and mixtures of two or more thereof.

  Aromatic polyisocyanates include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, m- or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), 2,4′- or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI {crude diaminophenylmethane [formaldehyde and aromatic amine ( Aniline) or a condensation product thereof; a mixture of diaminodiphenylmethane and a small amount (for example 5 to 20% by weight) of a trifunctional or higher polyamine] phosgenation product: polyallyl polyisocyanate (PAPI)}, 1,5 -Naphthylene diisocyanate, 4,4 ', 4 "-Tripheny Triisocyanate, m- or p- isocyanatophenyl sulfonyl isocyanate and mixtures thereof.

Examples of the aliphatic polyisocyanate include a chain aliphatic polyisocyanate and a cyclic aliphatic polyisocyanate.
Examples of chain aliphatic polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and these And the like.
Cycloaliphatic polyisocyanates include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl). ) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate and mixtures thereof.

  As the modified polyisocyanate, a modified product containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a burette group, a uretdione group, a uretoimine group, an isocyanurate group and / or an oxazolidone group is used. (Urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and mixtures thereof [for example, mixtures of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)] and the like.

  Of the polyisocyanates (14), aromatic polyisocyanates having 6 to 15 carbon atoms and aliphatic polyisocyanates having 4 to 15 carbon atoms are preferred, and TDI, MDI, HDI, hydrogenated MDI and IPDI.

Examples of the polyamine (15) include aliphatic polyamines having 2 to 18 carbon atoms and aromatic polyamines (6 to 20 carbon atoms).
Examples of the aliphatic polyamine having 2 to 18 carbon atoms include chain aliphatic polyamines, alkyl (carbon number 1 to 4) or hydroxyalkyl (carbon numbers 2 to 4) substituents thereof, and cyclic aliphatic polyamines.

  Examples of chain aliphatic polyamines include alkylene diamines having 2 to 12 carbon atoms (such as ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine and hexamethylene diamine) and polyalkylenes (having 2 to 6 carbon atoms) [diethylene triamine, imino. Bispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.].

  Examples of alkyl (carbon number 1 to 4) or hydroxyalkyl (carbon number 2 to 4) substitution products of chain aliphatic polyamines include dialkyl (carbon number 1 to 3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, and the like.

  Cycloaliphatic polyamines include alicyclic polyamines having 4 to 15 carbon atoms {1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline) and 3 , 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like} and a heterocyclic polyamine having 4 to 15 carbon atoms [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, etc.] and the like.

  Aromatic polyamines (6 to 20 carbon atoms) include unsubstituted aromatic polyamines and alkyl groups (alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n- or isopropyl and butyl groups). Aromatic polyamines having aromatic polyamines, electron-withdrawing groups (halogen atoms such as Cl, Br, I and F; alkoxy groups such as methoxy and ethoxy groups; and nitro groups) and aromatic polyamines having secondary amino groups, etc. Can be used.

  As the unsubstituted aromatic polyamine, 1,2-, 1,3- or 1,4-phenylenediamine, 2,4′- or 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 and These mixtures etc. are mentioned.

  The aromatic polyamine having an alkyl group (alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n- or isopropyl group and butyl group) includes 2,4- or 2,6-tolylenediamine, crude Tolylenediamine, 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-trie 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′-tetra Methyl-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'-diaminodiphenyl sulfone, and mixtures thereof Is mentioned.

  Aromatic polyamines having electron-withdrawing groups (halogen atoms such as Cl, Br, I and F; alkoxy groups such as methoxy and ethoxy groups; and nitro groups) include 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-chlorophene) ) 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-methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4'-methylenebis (2-bromoaniline), 4,4'- Examples include methylenebis (2-fluoroaniline) and 4-aminophenyl-2-chloroaniline.

As the aromatic polyamine having a secondary amino group, a part or all of —NH ₂ of the unsubstituted aromatic polyamine, the aromatic polyamine having an alkyl group, and the aromatic polyamine having an electron withdrawing group is —NH—R ′. (R ′ is an alkyl group, for example, a lower alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group) [for example, 4,4′-di (methylamino) diphenylmethane and 1-methyl- 2-methylamino-4-aminobenzene, etc.], polyamide polyamine: condensation of dicarboxylic acid (dimer acid, etc.) and excess (more than 2 moles per mole of acid) polyamines (the above alkylene diamine, polyalkylene polyamine, etc.) Low molecular weight polyamide polyamine: polyether polyamine: and polyether polyol (polyalkylene group) A hydride of a cyanoethylated product of a recall, etc.).

  Examples of polythiol (16) include alkanedithiols having 2 to 36 carbon atoms (ethylene dithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.) and the like.

  Examples of the primary and / or secondary monoamine (17) include alkylamines having 2 to 24 carbon atoms (such as ethylamine, n-butylamine, isobutylamine, diethylamine, and n-butyl-n-dodecylamine).

  Examples of the epoxy resin include ring-opened polymer of polyepoxide (18), polyepoxide (18) and active hydrogen-containing compound {water, diol (10), dicarboxylic acid (12), polyamine (15), polythiol (16), etc.} And polycured product of polyepoxide (18) and acid anhydride of dicarboxylic acid (12).

  The polyepoxide (18) used for this invention will not be specifically limited if it has two or more epoxy groups in a molecule | numerator. The polyepoxide (18) preferably has two epoxy groups in the molecule from the viewpoint of the mechanical properties of the cured product. The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide (18) is preferably 65 to 1,000, and more preferably 90 to 500. When the epoxy equivalent is 1,000 or less, the cross-linked structure becomes dense and physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are improved. On the other hand, those having an epoxy equivalent of less than 65 are synthesized. It is difficult.

Specific examples of the polyepoxide (18) include aromatic polyepoxy compounds and aliphatic polyepoxy compounds.
Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols.

Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyldi Glycidyl ether, tetramethylbiphenyl diglycidyl ether Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -T-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, phenol or Glycidyl ether of cresol novolak resin, glycidyl ether of limonenephenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, condensation reaction of phenol and glyoxal, glutaraldehyde, or formaldehyde And a polyglycidyl ether body of polyphenol obtained by a condensation reaction of resorcin and acetone.
Examples of the glycidyl ester of polyhydric phenol include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester.
Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine and N, N, N ′, N′-tetraglycidyldiphenylmethanediamine.
Further, as the aromatic polyepoxy compound, p-aminophenol triglycidyl ether, tolylene diisocyanate or a diglycidyl urethane compound obtained by the addition reaction of diphenylmethane diisocyanate and glycidol, obtained by reacting the two reactants with a polyol. And glycidyl group-containing polyurethane (pre) polymer and bisphenol A AO adduct diglycidyl ether.

  Examples of the aliphatic polyepoxy compound include a chain aliphatic polyepoxy compound and a cyclic aliphatic polyepoxy compound.

Examples of chain aliphatic polyepoxy compounds include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines.
Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Examples include 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. It is done.
Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate and diglycidyl pimelate.
Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine.
Examples of the aliphatic polyepoxy compound include a copolymer of diglycidyl ether and glycidyl (meth) acrylate.

Examples of the cycloaliphatic polyepoxy compound include trisglycidyl melamine, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3,4 -Epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6 -Methylcyclohexylmethyl) butylamine and dimer acid diglycidyl ester.
Moreover, as a cycloaliphatic polyepoxy compound, the hydrogenated thing of the said aromatic polyepoxide compound is also mentioned.

Examples of the polyamide resin include a lactam ring-opening polymer, a polycondensate of aminocarboxylic acid, a polycondensate of polycarboxylic acid and polyamine, and the like.
Polyimide resins include aliphatic polyimide resins (polymers obtained from aliphatic carboxylic dianhydrides and aliphatic diamines) and aromatic polyimide resins (aromatic carboxylic dianhydrides and aliphatic diamines or aromatic diamines). Etc.) and the like.
Examples of the silicon resin include polymers having a silicon-silicon bond, silicon-carbon bond, siloxane bond, or silicon-nitrogen bond in the molecular chain (polysiloxane, polycarbosilane, polysilazane, and the like).
Examples of the phenol resin include polymers obtained by condensation of phenols (phenol, cresol, nonylphenol, lignin, resorcin, catechol, etc.) and aldehydes (formaldehyde, acetaldehyde, furfural, etc.).
Examples of the melamine resin include a polymer obtained by polycondensation of melamine and formaldehyde.
Examples of urea resins include polymers obtained by polycondensation of urea and formaldehyde.
Examples of aniline resins include polymers obtained by polymerizing aniline and aldehydes under acidic conditions.
As ionomer resins, there are monomers having a polymerizable double bond (α-olefin and styrene monomer, etc.) and α, β-unsaturated carboxylic acids (acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic acid). Acid monomethyl ester, maleic anhydride, maleic anhydride monoethyl ester, etc.) and part or all of the carboxylic acid in the copolymer is carboxylate (potassium salt, sodium salt, magnesium salt, calcium salt, etc.) ) And the like.
Examples of the polycarbonate resin include condensates of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S) with phosgene or carbonic acid diester.

(B) may be a crystalline resin (b1) or an amorphous resin (b2), or a combination of (b1) and (b2). Of these, (b1) is preferred.
In the present invention, “crystallinity” means that the ratio (Tm / Ta) of the softening point (hereinafter abbreviated as Tm) and the maximum peak temperature of heat of fusion (hereinafter abbreviated as Ta) of 0. It is 8 to 1.55, and indicates that it has a clear endothermic peak, not a stepwise endothermic change in DSC. “Non-crystalline” means that the ratio of Tm to Ta (Tm / Ta) is greater than 1.55. Tm and Ta can be measured by the following method.
<Tm measurement method>
Using a Koka flow tester {for example, “CFT-500D” [manufactured by Shimadzu Corporation]}, a 1 g measurement sample is heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa is applied by a plunger. Is drawn from a nozzle having a diameter of 1 mm and a length of 1 mm, and a graph of “plunger lowering amount (flow value)” and “temperature” is drawn, corresponding to 1/2 of the maximum value of the plunger lowering amount. The temperature is read from the graph, and this value (temperature when half of the measurement sample flows out) is defined as Tm.
<Ta measurement method>
It is measured using a differential scanning calorimeter {for example, “DSC210” [manufactured by Seiko Denshi Kogyo Co., Ltd.]}.
As a pretreatment, a sample to be measured for Ta is melted at 130 ° C., then cooled at a rate of 1.0 ° C./min from 130 ° C. to 70 ° C., and then 0.5 ° C./70° C. to 10 ° C. Lower the temperature at the rate of minutes. Here, by DSC, the temperature is increased at a rate of temperature increase of 20 ° C./min and the change in endothermic heat is measured to draw a graph of “endothermic heat generation” and “temperature”. The endothermic peak temperature at is defined as Ta ′. When there are a plurality of peaks, the peak temperature having the largest endothermic amount is defined as Ta ′. Finally, the sample is stored at (Ta′−10) ° C. for 6 hours, and then stored at (Ta′−15) ° C. for 6 hours.
Next, after cooling the above sample by DSC to 0 ° C. at a temperature decrease rate of 10 ° C./min, the temperature was increased at a temperature increase rate of 20 ° C./min and the endothermic change was measured to draw a similar graph. The temperature corresponding to the maximum peak is defined as the maximum peak temperature (Ta) of heat of fusion.

The precursor (b0) of the resin (b) is not particularly limited as long as it can become the resin (b) by a chemical reaction. When the resin (b) is a vinyl resin, (b0) Examples thereof include monomers having a polymerizable double bond (which may be used alone or in combination).
When the resin (b) is a condensation resin (polyurethane resin, epoxy resin, polyester resin, etc.), (b0) includes a combination of a prepolymer (α) having a reactive group and a curing agent (β). It is done.

  When a monomer having a polymerizable double bond is used as the precursor (b0), as a method of reacting the precursor (b0) to obtain a resin (b), for example, an oil-soluble initiator and a monomer And the like. A method of dispersing and suspending an oil phase containing (X) and performing a radical polymerization reaction by heating can be mentioned.

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

Oil-soluble peroxide polymerization initiator (I):
Acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, parachlorobenzoyl peroxide, cumene peroxide, and the like.

Oil-soluble azo polymerization initiator (II):
2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2′-azobis (2-methylpropionate) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like.

Non-aqueous redox polymerization initiator (III):
Oil-soluble peroxides such as hydroperoxides, dialkyl peroxides and diacyl peroxides, and oil-soluble reducing agents such as tertiary amines, naphthenates, mercaptans, organometallic compounds (such as triethylaluminum, triethylboron and diethylzinc) And in combination.

  When the combination of the prepolymer (α) having a reactive group and the curing agent (β) is used as the precursor (b0), the “reactive group” possessed by (α) is a reaction with the curing agent (β). A possible group. In this case, as a method of forming the resin (b) by reacting the precursor (b0), (α) and (β) are dispersed in (X) and (α) and (β) are heated. The method etc. which are made to react and form resin particle (B) containing resin (b) are mentioned.

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] A combination in which the reactive group of (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and (β) is an active hydrogen group-containing compound (β1).
[2] A combination in which the reactive group of (α) is an active hydrogen-containing group (α2), and (β) is a compound (β2) that can react with the active hydrogen-containing group.
In the above 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), and an acid anhydride group (α1d). And acid halide groups (α1e) and the like. Of these, (α1a), (α1b) and (α1c) are preferred, and (α1a) and (α1b) are more preferred.
The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent.
Examples of the blocking agent include oximes (acetoxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, and methyl ethyl ketoxime); lactams (γ-butyrolactam, ε-caprolactam, and γ-valero Lactams, etc.); C1-C20 aliphatic alcohols (ethanol, methanol, octanol, etc.); phenols (phenol, m-cresol, xylenol, nonylphenol, etc.); active methylene compounds (acetylacetone, ethyl malonate, and acetoacetate) Ethyl etc.); basic nitrogen-containing compounds (N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.); and mixtures of two or more thereof Thing, and the like.
Of these, oximes are preferred, and methyl ethyl ketoxime is more preferred.

Examples of the structural unit of the reactive group-containing prepolymer (α) include polyether (αw), polyester (αx), epoxy resin (αy), and polyurethane (αz). Of these, (αx), (αy) and (αz) are preferred, and (αx) and (αz) are more preferred.
Examples of the polyether (αw) include polyethylene oxide, polypropylene oxide, polybutylene oxide, and polytetramethylene oxide.
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 condensates of bisphenols (such as bisphenol A, bisphenol F and bisphenol S) and epichlorohydrin.
Examples of polyurethane (αz) include a polyaddition product of diol (11) and polyisocyanate (15) and a polyaddition product of polyester (αx) and polyisocyanate (15).

As a method of incorporating reactive groups into polyester (αx), epoxy resin (αy), polyurethane (αz), etc.,
[1] A method of leaving a functional group of a constituent component at the terminal by using one of two or more constituent components in excess.
[2] A compound containing a functional group and a reactive group capable of reacting with the remaining functional group by leaving the functional group of the structural component at the terminal end by excessively using one of two or more structural components How to react.
Etc.
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, and a hydroxyl group-containing polyurethane prepolymer And an isocyanate group-containing polyurethane prepolymer and the like.
For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is preferably such that the ratio of the polyol component and the polycarboxylic acid component is the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 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 above method [2], an isocyanate group-containing prepolymer is obtained by reacting the preprimer obtained in the above method [1] with a polyisocyanate, and a blocked polyisocyanate is reacted with a blocked isocyanate group. A prepolymer is obtained, an epoxy group-containing prepolymer is obtained by reacting a polyepoxide, and an acid anhydride group-containing prepolymer is obtained by reacting a polyacid anhydride.
The amount of the compound containing a functional group and a reactive group is, for example, when the isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate, and the ratio of the polyisocyanate is an isocyanate group [NCO]. The equivalent ratio [NCO] / [OH] of the hydroxyl group [OH] of the hydroxyl group-containing polyester is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, and 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 preferably 1 or more, more preferably 1.5 to 3 on average, and particularly preferably 1.8 to 2 on average. .5. By setting it as the said range, the molecular weight of the hardened | cured material obtained by making it react with a hardening | curing agent ((beta)) becomes high.
The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000.
The Mw 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 (B) having a narrow particle size distribution can be obtained.

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

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

Examples of the polyol (β1b) include the same as the diol (11) and the trivalent to octavalent or higher polyol (12). Among these, diol (11) alone and a mixture of diol (11) and a small amount of polyol (12) are preferable.
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 the resin (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 monophenols (such as butyl mercaptan and lauryl mercaptan); monoisocyanates (such as lauryl isocyanate and phenyl isocyanate); and monoepoxides (such as butyl glycidyl ether).

The active hydrogen-containing group (α2) possessed by the reactive group-containing prepolymer (α) in the above combination [2] includes amino group (α2a), hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), mercapto group (Α2c), a carboxyl group (α2d), and an organic group (α2e) blocked with a compound from which they can be removed. Among these, (α2a), (α2b) and (α2e) are preferable, and (α2b) is more preferable.
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), polyacid anhydride (β2d), and polyacid halide (β2e). It is done. Of these, (β2a) and (β2b) are preferred, and (β2a) is more preferred.

Examples of the polyisocyanate (β2a) include those similar to the polyisocyanate (15), and preferred ones are also the same.
Examples of the polyepoxide (β2b) include those similar to 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). Among these, (β2c-1) alone and (β2c- 1) and a small amount of (β2c-2).
Examples of the dicarboxylic acid (β2c-1) include those similar to the dicarboxylic acid (13) and the trivalent to hexavalent or higher polycarboxylic acid (14), 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 acid halides (acid chloride, acid bromide, acid iodide, etc.) 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. . In addition, when a hardening | curing agent ((beta)) is water, water is handled as a bivalent active hydrogen compound.

The number average molecular weight (hereinafter abbreviated as Mn) of the resin (b) is preferably 1,000 to 5,000,000, and more preferably 2,000 to 500,000.
The Mn and weight average molecular weight (hereinafter abbreviated as Mw) of the resin in the present invention can be measured under the following conditions using gel permeation chromatography (GPC).
Apparatus (example): “HLC-8120” [manufactured by Tosoh Corporation]
Column (example): “TSK GEL GMH6” [manufactured by Tosoh Corporation] Measurement temperature: 40 ° C.
Sample solution: 0.25% by weight THF solution (insoluble matter filtered off with glass filter)
Solution injection volume: 100 μl
Detection apparatus: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (Molecular weight: 500, 1,050, 2,800, 5,970, 9,100,
18,100,37,900,96,400,190,000,355,000,
1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

The solubility parameter (hereinafter abbreviated as SP value) of (b) is preferably 7 to 18 (cal / cm ³ ) ^1/2 , more preferably 8 to 14 (cal / cm ³ ) ^1/2. Especially preferably, it is 9-14 (cal / cm < ³ >) ^<1/2 >.
In addition, SP value in this invention is the method by Fedors [Polym. Eng. Sci. 14 (2) 152, (1974)].

  The glass transition temperature (hereinafter abbreviated as Tg) of (b) is preferably 20 to 200 ° C, more preferably 40 to 150 ° C. Above 20 ° C., the storage stability of the particle (B) is good. In addition, Tg can be measured by the method (DSC) prescribed | regulated to ASTM D3418-82 using "DSC20, SSC / 580" [made by Seiko Electronic Industry Co., Ltd.].

  The softening start temperature of (b) is preferably 40 to 220 ° C, more preferably 50 to 200 ° C. If it is 40 degreeC or more, the long-term storage property of the resin particle (B) will be favorable. If it is 220 degrees C or less, since the fixing temperature at the time of using (B) as an electrophotographic toner can be lowered | hung, it is preferable. In addition, the softening start temperature in this invention can be measured using a flow tester.

The solvent (S) constituting the solvent solution of the resin (b) or the solvent solution of (b0) is not particularly limited as long as it can dissolve (b) and (b0). Hydrocarbon solvents (toluene, xylene, ethylbenzene, tetralin, etc.); aliphatic hydrocarbon solvents (n-hexane, n-heptane, n-decane, mineral spirits, cyclohexane, etc.); halogen solvents (methyl chloride, methyl bromide, iodine) Methyl chloride, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene, etc.); ester solvents (ethyl acetate, butyl acetate, methyl 2-hydroxyisobutyrate, methyl lactate, ethyl lactate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve) Acetate, methyl pyruvate and ethyl pyruvate); Tell solvent (diethyl ether, tetrahydrofuran, dioxane, dioxolane, ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.); ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-) Butyl ketone and cyclohexanone); alcohol solvents (methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol, 2,2,3,3-tetrafluoropropanol and Trifluoroethanol, etc.); amide solvents (dimethylformamide, dimethylacetamide, etc.); De solvent (dimethyl sulfoxide, etc.); heterocyclic compounds solvents (N- methylpyrrolidone) and a mixed solvent of two or more thereof. Moreover, the mixed solvent of these organic solvents and water can also be used.
Of (S), preferred are aliphatic hydrocarbon solvents, ester solvents, ether solvents and ketone solvents, and more preferred are n-hexane, n-heptane, n-decane, ethyl acetate, butyl acetate, acetone. And methyl ethyl ketone.

The SP value of the solvent (S) is preferably 9 to 16 (cal / cm ³ ) ^1/2 , more preferably 10 to 15 (cal / cm ³ ) ^1/2 .

The concentration of the resin (b) in the solvent solution of the resin (b) is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, based on the weight of the solvent solution of the resin (b).
The concentration of the resin (b) in the solvent solution of the precursor (b0) is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, based on the weight of the solvent solution of the precursor (b0). is there.

Examples of the non-aqueous medium (X) in the present invention include carbon dioxide (X1) in a liquid state or a supercritical state, a non-aqueous organic solvent (X2), and the like. Of these, (X1) is preferable.
In (X1), carbon dioxide in a liquid state is a triple point of carbon dioxide (temperature = −57 ° C., pressure 0.5 MPa) and carbon dioxide on a phase diagram represented by a temperature axis and a pressure axis of carbon dioxide. Represents carbon dioxide, which is the temperature / pressure condition of the portion surrounded by the gas-liquid boundary line passing through the critical point (temperature = 31 ° C., pressure = 7.4 MPa), the isotherm of the critical temperature, and the solid-liquid boundary line.
Among (X1), the carbon dioxide in the supercritical state represents carbon dioxide that is a temperature / pressure condition higher than the critical temperature (however, the pressure represents the total pressure in the case of a mixed gas of two or more components).

Examples of the non-aqueous organic solvent (X2) include solvents (S) that are not compatible with each other and separated or become cloudy when mixed with water at a weight ratio of 1: 1, and the solubility of the resin (b). Is 1% by weight or less. If the solubility of (b) is 1% by weight or less, it is preferable that the resin particles (B) are difficult to unite with each other. In addition, the solubility with respect to (X2) of (b) can be measured with the following method.
(B) A non-aqueous dispersion in which 10 g is dispersed in 90 g of (X2) is centrifuged at 3,000 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 (X2), and the mass of the residue is weighed. If the residual mass at this time is Wg, the solubility of the resin (G) in the non-aqueous organic solvent (X2) can be calculated from the following equation.
Solubility (% by weight) = [(W / w) / 10] × 100

There is no restriction | limiting in particular as a method of producing a dispersion (Y), For example, the following method is mentioned.
[1] A method of dispersing the resin (b), the solvent solution of the resin (b), the solvent solution of the precursor (b0) or (b0) in (X) by a dispersing machine or ultrasonic irradiation.
[2] In (X), resin (b), a solvent solution of resin (b), a solvent solution of precursor (b0) or (b0) is sprayed through a spray nozzle to form droplets, A method in which resin (b) in a droplet is supersaturated to precipitate resin particles (known as ASES: Aerosol Solvent Extraction System).
[3] From a coaxial multiple tube (double tube, triple tube, etc.), resin (b), solvent solution of resin (b), solvent solution of precursor (b0) or (b0), and (X) A method in which particles are obtained by simultaneously ejecting liquid droplets together with a high-pressure gas, an entrainer, etc., and applying external stress to the droplets to promote breakup (known as SEDS: Solution Enhanced Dispersion by Supercritical Fluids).

  The weight ratio of (b) and / or (b0) based on the weight of (X) is preferably 50% by weight or less, more preferably 30% by weight or less, and particularly preferably 0.1 to 20% by weight. . If it is this range, a resin particle (B) can be manufactured efficiently.

  The disperser in the method [1] is not particularly limited as long as it is generally an emulsifier or a commercially available disperser. For example, a batch emulsifier {“homogenizer” (manufactured by IKA), “ Polytron "(manufactured by Kinematica) and" TK auto homomixer "[manufactured by Tokushu Kika Kogyo Co., Ltd.]}, continuous emulsifier {" Ebara Milder "[manufactured by Ebara Corporation]," TK Philmix ”,“ TK Pipeline Homo Mixer ”[manufactured by Special Machine Industries Co., Ltd.],“ Colloid Mill ”[manufactured by Shinko Pantech Co., Ltd.],“ Slasher ”,“ Trigonal Wet Fine Crusher ”[Suntech Co., Ltd.] Product], “Capitoron” (manufactured by Eurotech) and “Fine Flow Mill” [manufactured by Taiheiyo Kiko Co., Ltd.]}, high-pressure emulsifier {“Microfluidizer” [manufactured by Mizuho Industry Co., Ltd.], Nanomizer "[manufactured by SG Engineering Co., Ltd.] and" APV Gaurin "(manufactured by Gaurin) etc.}, membrane emulsifier {" membrane emulsifier "[manufactured by Chilling Industries Co., Ltd.]}, vibration emulsifier {"Vibro mixer" [manufactured by Chilling Industries Co., Ltd.]}, ultrasonic emulsifier {"ultrasonic homogenizer" (manufactured by Branson) etc.}, etc. Among these, the batch type emulsifier, the continuous type emulsifier and the high pressure emulsifier are preferable from the viewpoint of the particle size distribution of (C), and more preferable are “APV Gaurin”, “Homogenizer”, “TK Auto Homo”. “Mixer”, “Ebara Milder”, “TK Fill Mix” and “TK Pipeline Homo Mixer”.

The oily liquid (G) in the present invention is [1] a melt of the resin (a), [2] a solvent solution of the resin (a), [3] a precursor (a0) of the resin (a), or [4 ] (A0) solvent solution.
Examples of the resin (a) include a crystalline resin (a1) and an amorphous resin (a2).
Of these, the crystalline resin (a1) is preferable.

  Examples of the crystalline resin (a1) include a crystalline polyester resin (a1-1), a crystalline polyurethane resin (a1-2), and a crystalline vinyl resin (a1-3).

As crystalline polyester resin (a1-1), what makes the said diol (10) and dicarboxylic acid (12) a structural unit is mentioned.
(A1-1) preferably has a total carbon number of 10 or more as structural units of the diol (10) and the dicarboxylic acid (12), more preferably 12 from the viewpoint of blocking resistance of the resin particles (C). The total number of carbon atoms is preferably 52 or less, more preferably 45 or less, and particularly preferably 45 or less, particularly preferably 14 or more, from the viewpoint of low-temperature fixability when used as a base particle of an electrophotographic toner. 40 or less, most preferably 30 or less. Moreover, as dicarboxylic acid (12), the C6-C30 aromatic dicarboxylic acid may be included if necessary.

  Examples of the crystalline polyurethane resin (a1-2) include those exemplified as the aliphatic diamine having 2 to 18 carbon atoms or the aromatic diamine having 6 to 20 carbon atoms among the diol (10) and the polyamine (15). And what makes the structural unit what was illustrated as diisocyanate among the said polyisocyanate (i) is mentioned.

As the crystalline vinyl resin (a1-3), a crystalline vinyl resin (a1-3-1) or (meth) acrylonitrile having an alkyl (meth) acrylate having an alkyl group having 12 to 50 carbon atoms as an essential constituent unit. A crystalline vinyl resin (a1-3-2) and a crystalline polyolefin (a1-3-3). “(Meth) acrylate” means acrylate or methacrylate, and “(meth) acrylonitrile” means acrylonitrile or methacrylonitrile.
In the alkyl (meth) acrylate having 12 to 50 carbon atoms in the alkyl group constituting (a1-3-1), the alkyl group has 14 carbon atoms from the viewpoint of blocking resistance of the resin particles (C). The above are preferable, more preferably 18 or more, and 40 or less are preferable from the viewpoint of low-temperature fixability when used as base particles of an electrophotographic toner, and more preferably 30 or less.
The content of the alkyl (meth) acrylate having 12 to 50 carbon atoms in the alkyl group in (a1-3-1) as a constituent unit is preferably 40% by weight based on the weight of (a1-3-1). More preferably, it is 45% by weight or more, particularly preferably 60% by weight or more.

  The content of (meth) acrylonitrile in (a1-3-2) as a structural unit is preferably 0.01 to 40% by weight based on the weight of (a1-3-1), more preferably 0.8. It is 05 to 35% by weight, particularly preferably 0.1 to 30% by weight.

  Examples of (a1-3-3) include polyethylene and polypropylene.

  Among (a1), (a1-3) is preferable, and (a1-3-1) is more preferable.

  The melting point of (a1) is preferably 40 to 110 ° C, more preferably 45 to 100 ° C, and particularly preferably 50 to 90 ° C. When the melting point of (a1-1) is 50 ° C. or higher, the blocking resistance of the resin particles (C) is improved. When the temperature is 110 ° C. or lower, the low-temperature fixability when (C) is used as the base particle of the electrophotographic toner is good. In addition, melting | fusing point in this invention means the temperature (degreeC) of the endothermic peak by melting at the first temperature rising measured by DSC based on JIS-K7122 (1987) "Method for measuring the transition heat of plastic".

The crystallinity of (a1) is preferably 20 to 95%, more preferably 30 to 80%, from the viewpoint of suppression of swelling by (X) and adsorptivity to the resin particles (B). The degree of crystallinity can be calculated from the area of the endothermic peak using DSC, the heat of fusion [ΔHm (J / g)], and calculated by the following formula based on the measured ΔHm.
Crystallinity (%) = (ΔHm / a) × 100
In the formula, a is the heat of fusion when extrapolated so that the crystallinity is 100%.

  Mn in (a1) is preferably 1,000 or more, more preferably 1,500 or more, and particularly preferably 2,000 or more, from the viewpoint of resin elasticity. Further, from the viewpoint of melt viscosity, it is preferably 1,000,000 or less, more preferably 500,000 or less, and particularly preferably 300,000 or less.

  Non-crystalline resin (a2) includes non-crystalline vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide, polyimide, silicone resin, fluororesin, phenol resin, melamine resin, polycarbonate, cellulose, and mixtures thereof. Is mentioned.

  The resin (a) may be a combination of (a1) and (a2). The melting point of the mixture of (a1) and (a2) is preferably 50 to 150 ° C. The content of (a2) when (a1) and (a2) are used in combination is preferably 0 to 50% by weight based on the total weight of (a1) and (a2). (F) may be fine particles obtained by coating (a2) with (a1).

  The solvent constituting the solvent solution of the resin (a) or the solvent solution of (a0) is not particularly limited as long as it dissolves (a) or (a0), and the same as the solvent (S) can be used. Can be mentioned. Of these, ester solvents and ether solvents are preferred.

The concentration of the resin (a) in the solvent solution of the resin (a) is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, based on the weight of the solvent solution of the resin (a).
The concentration of the resin (b) in the solvent solution of the precursor (a0) is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, based on the weight of the solvent solution of the precursor (a0). is there.

  The composite dispersion (Z) in the present invention is obtained by mixing the dispersion (Y) and the oily liquid (G).

  The resin particle (C) in the present invention is formed by adhering the resin (a) to the surface of the resin particle (B) containing the resin (b). The resin particles (C) can be obtained by solidifying the composite dispersion (Z). That is, by solidifying (Z), the resin (a) is adhered to the surface of the resin particle (B), and the resin particle (C) is formed.

When the non-aqueous medium (X) is carbon dioxide (X1) in a liquid state or a supercritical state, the method for solidifying the composite dispersion (Z) is [1] reducing the pressure of the composite dispersion (Z). [2] a method of solidifying by pressurizing the pressure of the composite dispersion (Z) and then reducing the pressure; [3] when (Z) contains (a0), polymerization of (a0) And a method of solidifying (Z) by reaction.
In the above method [1], the solvent (S) in (Z) is removed by reducing the pressure of (Z), and the resin (a) is adhered to the surface of the resin particles (B). Particles (C) are formed.
In the above method [2], by adding (X1) to (Z) and pressurizing the pressure (Z), the resins (a) and (b) are likely to precipitate in (Z). Next, by reducing the pressure of (Z), the solvent (S) in (Z) is removed, and the resin (a) is adhered to the surface of the resin particles (B) to form resin particles (C). Is done.
In the above method [3], the resin particles (C) are formed by attaching (a0) to the surface of the resin particles (B) and converting (a0) to (a) on the surface of (B). Is done.

  In the case where the non-aqueous medium (X) is (X1), the pressure of the composite dispersion (Z) is preferably 7 MPa or more from the viewpoint of satisfactorily dispersing (C) in (X1). From the viewpoint of cost and operating cost, it is 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.

  In the production method of the present invention, the temperature and pressure of the operation performed in (X) should be set within a range in which (G) does not dissolve in (X) and (G) can aggregate and unite. Is preferred. Usually, the lower the temperature and the lower the pressure, the more the (P) tends not to dissolve in (X), and the higher the temperature and the higher the pressure, the easier (P) tends to aggregate and coalesce. The same applies to the dispersion (X0) and the dispersion (X1).

  In the production method of the present invention, the operation performed in (X) is preferably performed at the temperature described below. That is, 30 ° C. or higher is preferable to prevent carbon dioxide from undergoing a phase transition in the pipe during decompression and block the flow path, and 200 ° C. or lower to prevent thermal deterioration of (C). preferable. More preferably, it is 30-150 degreeC, More preferably, it is 34-130 degreeC, Especially preferably, it is 35-100 degreeC, Most preferably, it is 40 degreeC-80 degreeC. The same applies to the temperature of the dispersion (X0) and the dispersion (X1). The operation performed in (X) can be performed at a temperature equal to or higher than the Tg or melting point of (a), but is preferably performed at a temperature lower than Tg or lower than the melting point.

(X) in the production method of the present invention appropriately contains other substances (Y) in order to adjust physical property values (viscosity, diffusion coefficient, dielectric constant, solubility, interfacial tension, etc.) as a dispersion medium. Often, (Y) includes inert gases such as nitrogen, helium, argon and air.
The weight ratio of (X) based on the total weight of (X) and (Y) is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.

When the oily liquid (G) is a precursor solution (a0) of the resin (a) or a solvent solution of (a0), (Z) can be solidified by (a0) polymerization reaction (a0). A method of converting to (a) is mentioned.
Examples of the polymerization reaction of (a0) include the same ones as exemplified as the method for converting the precursor (b0) of (b) into (b).

After forming (C), it is preferable to perform a step of removing or reducing (X) as necessary. However, when (X) is (X1) and (S1) is contained in (X1), when the container is decompressed as it is, (S) dissolved in (X1) is condensed and resin particles (C ) May be re-dissolved, or the resin particles (C) may be joined together when the resin particles (C) are collected.
As a method of removing or reducing (S), for example, (X1) is further mixed with the composite dispersion (Z), and (S) is extracted into the phase (X1) from (Z). It is preferable to replace (X1) containing () with (X1) not containing (S), and then reduce the pressure.

  When mixing (X1) with the composite dispersion (Z), (X1) at a pressure higher than (Z) may be added, and (Z) is added into (X1) at a pressure lower than (Z). However, the latter is preferred from the viewpoint of ease of continuous operation. The amount of (X1) mixed with (Z) is preferably from 1 to 50 times, more preferably from 1 to 40 times, most preferably from the viewpoint of preventing coalescence of the resin particles (C). 1 to 30 times. By removing or reducing (S) contained in the resin particles (C) as described above, and then removing (X1), it is possible to prevent the resin particles (C) from being combined. .

  As a method of replacing (X1) containing (S) with (X1) not containing (S), the resin particles (C) are once captured by a filter or cyclone, and then the pressure is maintained while (S) A method of circulating (X1) until it is completely removed can be mentioned. The amount of (X1) to be circulated is preferably 1 to 100 times, more preferably 1 to 50 times, and most preferably 1 to 30 times the volume of (Z).

As a method of removing the (X) from the composite dispersion (Z) to obtain the resin particles (C),
[1] A method of drying (Z) under reduced pressure or normal pressure.
[2] A method in which (Z) is solid-liquid separated by a centrifuge, a spatula filter, a filter press or the like, and the obtained powder is dried.
[3] A method of freeze-drying (Z).
Etc.
In the above [1] and [2], when drying the obtained resin particles (C), known equipment such as a fluidized bed dryer, a vacuum dryer, and a circulating dryer can be used.
Moreover, it can classify | classify using a wind classifier etc. as needed, and can also be set as predetermined particle size distribution.
In addition, (C) in which (a) on the surface of (B) is formed into a film may be formed during the manufacturing process such as the solvent removal process.

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

In order to adhere the resin (a) to the surface of (B), it is necessary to control the adsorption force of (a) to (B), and specifically, it can be controlled by the following method.
[1] When the resin (a) and the resin particles (B) have positive and negative charges, the adsorption force is improved. In this case, the greater the charge of each of the resin (a) and the resin particles (B), the stronger the adsorption force and the higher the coverage of the resin (a) with respect to the resin particles (B). The resin (a) and the resin particle (B) may have an acidic functional group or a basic functional group inside or on the surface in order to increase the charge. Examples of the acidic functional group include a carboxylic acid group and a sulfonic acid group. Examples of basic functional groups include primary amino groups, secondary amino groups, and tertiary amino groups.
[2] When the resin (a) and the resin particles (B) have the same polarity (both positive or both negative), the coverage tends to decrease. In this case, in general, when a surfactant and / or an oily polymer [particularly those having a reverse charge to the resin (a) and the resin particles (B)] are used, the adsorptive power becomes strong and the coverage becomes high.
[3] When the difference between the SP values of the resin (a) and the resin (b) is reduced, the adsorption force is increased and the coverage is increased.

  When the resin (a) contains (a1), depending on the composition of (a1) and (B), the resin (a) fixed to the surface of (B) may be converted into a film during the production process. ) May be formed on the surface of (a).

  When the resin particles (C) contain the crystalline resin (b1), after forming the resin particles (B), if necessary, at a temperature lower than the melting point of (b1), preferably by 50 ° C. or more, ( The resin (a) fixed on the surface of the resin particles (B) is melted by heating (C) at a temperature lower than the melting point of b1), more preferably at a temperature lower than 10 ° C., particularly preferably at a temperature higher than the melting point. The film derived from (a) can be formed to produce the resin particles (C). From the viewpoint of suppressing aggregation of (C), the heating time is preferably 0.01 to 1 hour, and more preferably 0.05 to 0.7 hour.

The resin particles (C) finally obtained by the production method of the present invention are obtained by fixing the resin (a) on the surface of (B), forming a film derived from (a), one of (a) Any part of which the film is formed into a film may be used.
In addition, the surface state and shape of (C) can be observed with the photograph which expanded the surface of the resin particle 10,000 times or 30,000 times, for example using a scanning electron microscope (SEM).

From the viewpoints of particle size uniformity, powder fluidity, storage stability, etc., 5% or more of the surface of the resin particles (B) is a film derived from the resin (a) or (a). It is preferably covered, more preferably 30% or more. The surface coverage can be determined based on the following equation from image analysis of an image obtained with a scanning electron microscope (SEM).
Surface coverage (%) = [(B) surface area of the portion covered with the film derived from (a) or (a) / {(the portion covered with the film derived from (a) or (a) ( B) surface area + (B) exposed surface area}] × 100

  In the resin particles (C) obtained by the production method of the present invention, the weight ratio of the resin (a) and the resin particles (B) is preferably (0.1: 99.9) to (30:70), More preferably, it is (0.2: 99.8) to (20:80). Within this range, the storage stability of (C) and the low-temperature fixability when (C) is used for an electronic toner can be satisfied.

The resin particles (C) obtained by the production method of the present invention are obtained by changing the particle diameters of the resin (a) and the resin particles (B) and the coverage of the resin particles (B) by the resin (a). Desirable irregularities can be imparted to the surface. Further, 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, it is preferable that the BET specific surface area of (C) is 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 Co., Ltd.] (measurement gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen) ). Similarly, from the viewpoint of powder flowability, 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 Co., Ltd.].

The shape of the resin particles (C) is preferably spherical from the viewpoints of fluidity and melt leveling.
(C) preferably has an average circularity of 0.96 to 1.0, more preferably 0.97 to 1.0, and particularly preferably 0.98 to 1.0. The average circularity in (C) is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. The average circularity of (C) can be measured using a flow type particle image analyzer “FPIA-2000” [manufactured by Sysmex Corporation].

The volume average particle size of the resin particles (C) of the present invention is preferably 3 to 10 μm, more preferably 4 to 8 μm, from the viewpoint of image resolution when used as a base particle of an electrophotographic toner. is there.
The particle size distribution [volume average particle diameter (Dv) / number average particle diameter (Dn)] of (C) is preferably 1.0 to 1.25, more preferably 1.0 to 1.21.

  When the resin particle (C) of the present invention is used as a base particle of an electrophotographic toner, the resin particle (C) contains an additive for an electrophotographic toner such as a release agent, a charge control agent and a fluidizing agent. These may be used, and these may be used in combination.

Examples of the release agent include polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and a mixture thereof. Tm measured with a flow tester of the release agent is preferably 50 to 170 ° C.
Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides by oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid and maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl of 1 to 18 carbon atoms) ester and Maleic acid alkyl (C1-18 alkyl) copolymers of an ester, etc.] or the like, and Sasol wax.
Examples of natural waxes include carnauba wax, montan wax, paraffin wax, and rice wax.
Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol. Examples of the fatty acid having 30 to 50 carbon atoms include triacontanoic acid.

  Charge control agents include quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, salicylic acid metal salts, benzylic acid boron complexes, sulfonic acid group-containing polymers, fluorine-containing polymers, and halogen-substituted aromatic rings. Examples thereof include polymers.

Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder.
The fluidizing agent is preferably added after the formation of the base particles of the electrophotographic toner.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

<Production Example 1> [Preparation of resin (b1) solution]
In a reaction vessel equipped with a cooling pipe, a thermometer, a stirrer, a dehydrator and a nitrogen introduction pipe, 191 parts by weight of PO3 molar adduct of bisphenol A, 155 parts by weight of EO2 molar adduct of bisphenol A, 115 parts by weight of adipic acid and 1 part by weight of tetrabutoxy titanate was added and reacted at 230 ° C. under a nitrogen stream for 5 hours while distilling off the generated water. Next, the reaction was carried out under a reduced pressure of 0.007 to 0.026 MPa. When the acid value reached 2, the mixture was cooled to 180 ° C., 15 parts by weight of trimellitic anhydride was added, and the reaction was taken out for 2 hours under sealed at atmospheric pressure. Resin (b1) was obtained. Resin (b1) had Tg of 12 ° C., Mn of 3,200, and Mw of 7,100.
Into a reaction vessel equipped with a condenser, a thermometer and a stirrer, 100 parts by weight of resin (b1) and 100 parts by weight of acetone are added, heated to 70 ° C., stirred and uniformly dissolved, and further cooled to room temperature. [Resin (b1) solution] was obtained.

<Production Example 2> [Preparation of resin (a1) solution]
In a reaction vessel equipped with a thermometer and a stirrer, 683 parts by weight of water, 11 parts by weight of EO adduct sulfate sodium salt “Eleminol RS-30” [manufactured by Sanyo Chemical Industries, Ltd.], 139 weights of styrene Parts, 138 parts by weight of methacrylic acid, 184 parts by weight of butyl acrylate, and 1 part by weight of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. Next, the temperature was raised to 75 ° C., and the reaction was performed at the same temperature for 5 hours. Further, 30 parts by weight of a 1% by weight aqueous ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 5 hours to give a vinyl resin (a copolymer of styrene-methacrylic acid-butyl methacrylate-methacrylic acid EO adduct sulfate sodium salt). An aqueous dispersion was obtained. This aqueous dispersion was dried with a vacuum dryer at 130 ° C. for 2 hours to obtain a resin (a1). The Tg of (a1) was 98 ° C.
In a reaction vessel equipped with a condenser, a thermometer and a stirrer, (a1) 50 parts by weight and 450 parts by weight of methanol are charged, heated to 50 ° C., stirred and uniformly dissolved, and further cooled to room temperature [ Resin (a1) solution] was obtained.

<Production Example 3> [Preparation of oily liquid (G1)]
In a beaker, 1,000 parts by weight of acetone, 100 parts by weight of the dispersant “Ionet S-85” [Sorbitan trioleate, manufactured by Sanyo Chemical Industries, Ltd.], 200 parts by weight of the resin (a1) solution obtained in Production Example 2 Was stirred at 12,000 rpm using a TK auto homomixer [manufactured by Tokushu Kika Kogyo Co., Ltd.] at 25 ° C. and uniformly dispersed to obtain an oily liquid (G1). The volume average particle diameter of (G1) was 0.3 μm.

<Example 1> [Preparation of resin particles (C1)]
Into a pressure vessel equipped with a thermometer, stirrer, pressure gauge and carbon dioxide introduction line, 10 parts by weight of the resin (b1) solution prepared in Production Example 1 is introduced, and carbon dioxide is introduced while stirring at 15 ° C. When the pressure in the container reached 6 MPa, the introduction of carbon dioxide was stopped, and stirring was continued as it was for 30 minutes to prepare a liquid carbon dioxide dispersion (Y1) of resin particles (B1). The amount of carbon dioxide introduced at this time was 30 parts by weight.
Next, 20 parts by weight of the oily liquid (G1) is transferred into the liquid carbon dioxide dispersion (Y1) of the resin particles (B1) while adjusting the inside of the container to maintain 8 MPa and 15 ° C. using a pressure pump. And stirred for 30 minutes. Thereafter, the inside of the container was maintained at 8 MPa and 15 ° C., carbon dioxide containing methanol was discharged while introducing carbon dioxide, and methanol was removed to obtain a composite dispersion (Z1). Carbon dioxide was released from the container containing the composite dispersion (Z1) to atmospheric pressure, the solid content was taken out of the container, washed with hexane and dried to obtain resin particles (C1).

<Comparative Production Example 1> [Preparation of comparative oily liquid (G′1)]
After mixing 900 parts by weight of n-decane and 200 parts by weight of the resin (a1) solution, zirconia beads having a particle diameter of 0.3 mm were used with a bead mill “Dynomill Multilab” [manufactured by Shinmaru Enterprises Co., Ltd.]. Grinding was performed to obtain a comparative oil phase liquid (G′1). The volume average particle diameter of (G′1) was 0.2 μm.

<Comparative Example 1> [Preparation of Comparative Resin Particles (C′1)]
Into a beaker, 80 parts by weight of the resin (b1) solution obtained in Production Example 1 and 4 parts by weight of water were added, stirred at 8,000 rpm using a TK auto homomixer at 50 ° C., and uniformly dispersed. A resin solution (o1) was obtained.
In a separate beaker, 200 parts by weight of n-decane, 25 parts by weight of the dispersant “Ionet S-85”, and 70 parts by weight of a comparative oil phase liquid (G′1) are added, and a TK auto homomixer is used at 25 ° C. While stirring at 12,000 rpm, 80 parts by weight of the resin solution (o1) was added and stirred for 3 minutes. Next, this mixed liquid is transferred to a reaction vessel equipped with a stirrer and a thermometer, heated to 45 ° C. to remove acetone, and resin particles (B) in which the resin (a1) contains the resin (b1). A dispersion of comparative resin particles (C′1) adhering to the surface was obtained. Next, while cooling the dispersion of (C′1) to 5 ° C., the solid content was separated by suction filtration, washed with hexane cooled to 5 ° C., and then dried under reduced pressure to give comparative resin particles (C′1). Got.

Tg, Mn, and Mw of the resin (a1) and the resin (b1) were measured by the above method.
The volume average particle diameters of the oily liquids (G1), (G′1), the resin particles (C1), and (C′1) are those dispersed in an aqueous sodium dodecylbenzenesulfonate solution (concentration: 0.1% by weight). It measured using the particle diameter measuring apparatus "LA-920" [made by Horiba, Ltd.].
The pressure fixability and heat resistant storage stability of the resin particles (C1) and (C′1) were evaluated by the following methods. The evaluation results are shown in Table 1.

[Pressure fixability]
Add 1.0% by weight of “Aerosil R972” [manufactured by Nippon Aerosil Co., Ltd.] to each of (C1) and (C′1) based on the weight of (C1) or (C′1), and use a mixer. The toner for evaluation was prepared by mixing “Aerosil R972” uniformly on the (C1) and (C′1) surfaces. The obtained toner for evaluation was uniformly placed on the paper surface so as to be 0.6 mg / cm ² . At this time, the resin particles were placed on the paper surface using a printer from which the heat fixing machine was removed (other methods may be used as long as the powder can be placed uniformly at the above-mentioned weight density). Cover this paper with release paper, press it at 25 ° C and 1.5 MPa using a desktop test press "SA-302" (manufactured by Tester Sangyo Co., Ltd.), rub the fixed image with your finger, and press according to the following criteria. Fixability was evaluated.
A: Fixed image does not peel at all O: Less than 5% of the fixed image area peels Δ: 5% to 30% of the fixed image area peels ×: More than 30% of the fixed image area peels off ××: All fixed images are peeled off

[Heat resistant storage stability]
10 g of each of the resin particles (C1) and (C′1) was collected in a 30 ml glass screw tube having a diameter of about 3 cm. The glass screw tube containing the resin particles was allowed to stand for 15 hours in a thermostat controlled at 50 ° C., and the heat resistant storage stability was evaluated according to the following criteria depending on the degree of blocking.
○: Blocking does not occur △: Blocking occurs, but it is easily loosened by applying force with fingers, etc. ×: Blocking occurs, and even if force is applied with fingers, etc.

  As shown in Table 1, the resin particles (C1) obtained by the production method of the present invention are superior in pressure fixability and heat-resistant storage stability compared to the resin particles (C′1) of Comparative Example 1. Is clear.

By the production method of the present invention, core-shell type resin particles having a narrow particle size distribution can be obtained, and the obtained resin particles are excellent in pressure fixability and heat-resistant storage stability. Additives, cosmetic additives, paper coating additives, slush molding resins, powder coatings, electronic component manufacturing spacers, standard particles for electronic measuring instruments, electronic paper particles, medical diagnostic carriers, electroviscous It is useful as particles and other resin particles for molding.

Claims (4)

  Resin particles (C) characterized in that a dispersion (Y) and an oily liquid (G) are mixed to obtain a composite dispersion (Z), and then (Z) is solidified to obtain resin particles (C). ) In which the dispersion (Y) is a non-aqueous medium (resin (b), a solvent solution of the resin (b), a precursor (b0) of the resin (b) or a solvent solution of (b0). X) is a dispersion in which the oily liquid (G) is obtained by melting the resin (a), a solvent solution of the resin (a), a precursor (a0) of the resin (a), or ( resin particles (C), which is a solvent solution of a0), and the resin particles (C) are resin particles in which the resin (a) is attached to the surface of the resin particles (B) containing the resin (b) Manufacturing method.   The resin according to claim 1, wherein the non-aqueous medium (X) is liquid or supercritical carbon dioxide (X1), and the composite dispersion (Z) is solidified by reducing the pressure. A method for producing particles (C).   The non-aqueous medium (X) is carbon dioxide (X1) in a liquid or supercritical state, and the composite dispersion (Z) is solidified by pressurizing the pressure and then depressurized. The manufacturing method of the resin particle (C) of description. The oily liquid (G) is the solvent solution of the precursor (a0) or (a0) of the resin (a), and (Z) is solidified by the polymerization reaction of (a0), and then the non-aqueous medium (X) is removed. The manufacturing method of the resin particle (C) in any one of Claims 1-3 characterized by the above-mentioned.