JP2009057487A - Resin particles and production method of resin particles - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method of resin particles having a uniform particle diameter excellent in charging characteristics, heat resistance storage stability and thermal property. <P>SOLUTION: This production method of resin particles (D) comprises: mixing an aqueous dispersion (W) containing resin particles (A) of a first resin (a) and a coagulant (E) with a second resin (b) or an organic solvent solution thereof or with a precursor (b0) of (b) or an organic solvent solution (O) thereof to disperse (O) in (W); optionally, reacting (b0), to form resin particles (B) of (b) in (W) and to form an aqueous dispersion (X1) of resin particles (C), in which a coating film (P) containing (A) or (a) is attached to the surface of (B); separating-removing and/or dissolving-removing at least a part of (A) or (P) on the surface of (C) to obtain an aqueous dispersion (X2) of resin particles (D) in which (B) is contained or a part of the surface of (B) is coated with (A) or (P); and further, removing the aqueous medium. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to resin particles and a method for producing the same. More specifically, the present invention relates to resin particles useful for various applications such as powder paints, electrophotographic toners, electrostatic recording toners, and the like, and methods for producing the same.

As resin particles having a uniform particle size and excellent electrical characteristics, thermal characteristics, chemical stability, and the like, resin particles obtained using polymer fine particles as a dispersion stabilizer are known (see Patent Document 1). ).
JP 2002-284881 A

However, in this method using polymer fine particles, it may remain and adhere to the surface of the resin, resulting in an inhibitor of fixing and charging. For this reason, the toner used in powder coatings, electrophotography, electrostatic recording, electrostatic printing, etc. can sufficiently exhibit the performance of the main resin (charging characteristics, heat-resistant storage stability, low-temperature fixability, etc.) Could not always be said.
The present invention has been made in view of the above circumstances in the prior art. That is, an object of the present invention is to provide resin particles having a uniform particle size excellent in charging characteristics, heat-resistant storage stability, and thermal characteristics.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention relates to an aqueous dispersion (W) containing the resin particles (A) comprising the first resin (a) and the flocculant (E), the second resin (b) or an organic solvent solution thereof, or When the resin (b) precursor (b0) or its organic solvent solution (O) is mixed, (O) is dispersed in (W), and (b0) or its organic solvent solution is used, Furthermore, the resin particles (A) or the resin (a) are formed on the surface of the resin particles (B) obtained by reacting (b0) to form the resin particles (B) made of (b) in (W). In the aqueous dispersion (X1) of the resin particles (C) to which the coating (P) made of is attached, at least a part of (A) or (P) on the surface of (C) is separated and / or dissolved and removed. , (B), or a part of the surface of (B) is (A) or ( ) To obtain an aqueous dispersion (X2) of the resin particles (D) coated with the resin particles (D), and further to remove the aqueous medium from (X2); and a BET value obtained by the above method; Resin particles having a specific surface area of 0.5 to 5.0 m ² / g.

The method for producing resin particles of the present invention and the resin particles obtained therefrom have the following effects.
1. Excellent thermal and charging properties and uniform particle size.
2. Excellent heat storage stability and powder flowability.
3. Since it can be easily produced without using a surfactant and the resin particles can be easily washed, it can be produced at low cost with little drainage.
4). Excellent particle surface smoothness.

  As the first resin (a) used in the present invention, a resin that can form the aqueous dispersion (W) may be selected. Any resin can be used as long as it is such a resin, and it is thermoplastic. Alternatively, a thermosetting resin may be used.

  Examples of the resin (a) include vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, and the like. Can be mentioned. As the resin (a), two or more of the above resins may be used in combination. Among these, from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained, vinyl resins, polyester resins, polyurethane resins, epoxy resins, and combinations thereof are more preferable, and vinyl resins are more preferable.

In order to obtain an aqueous dispersion (W) of fine spherical resin particles (A), the resin (a) preferably contains a carboxyl group. At least a part of the carboxyl group may be neutralized with a base. The base neutralization rate of the carboxyl group is preferably 20 to 100 equivalent%, and more preferably 40 to 100 equivalent%.
The content of the carboxyl group [the content converted to a carboxyl group (—COOH group when neutralized with a base)] is preferably 0.1 to 30% based on the weight of (a). The lower limit is more preferably 0.5%, particularly preferably 1%, most preferably 3%, and the upper limit is further preferably 25%, particularly preferably 22%, most preferably 20%.
When the base neutralization rate and the carboxyl group content are at least the lower limit of the above range, the resin (a) is easily dispersed in the aqueous medium, and the aqueous dispersion (W) of fine spherical resin particles (A) is obtained. Can be easily obtained. Further, the charging characteristics of the obtained resin particles (D) are improved.
In the above and the following, “%” means “% by weight” unless otherwise specified.

Examples of the base that forms the neutralized salt include ammonia, monoamine having 1 to 30 carbon atoms, polyamine (16), quaternary ammonium, alkali metal (sodium, potassium, etc.), and alkaline earth metal (calcium salt) described later. , Magnesium salts, etc.).
Examples of the monoamine having 1 to 30 carbon atoms include primary and / or secondary amines having 1 to 30 carbon atoms (ethylamine, n-butylamine, isobutylamine, etc.), and tertiary amines having 3 to 30 carbon atoms (trimethylamine, triethylamine). , Lauryl dimethylamine, etc.). Examples of the quaternary ammonium include trialkylammonium having 4 to 30 carbon atoms (such as lauryltrimethylammonium).
Among these, preferred are alkali metals, quaternary ammoniums, monoamines and polyamines, more preferred are sodium and monoamines having 1 to 20 carbon atoms, and particularly preferred are 3 having 3 to 20 carbon atoms. Grade monoamine.
Moreover, in the case of vinyl resin and polyester resin, the preferable carbon number of the monomer which contains the carboxyl group which forms them, or its salt is 3-30, More preferably, it is 3-15, Most preferably, it is 3-8. .

To obtain an aqueous dispersion (W) of fine spherical resin particles (A), and to obtain an aqueous dispersion (X1) of resin particles (C) having excellent heat-resistant storage stability and charging characteristics and a uniform particle size In addition, the resin (a) preferably contains a sulfonate anion group (—SO ₃ ⁻ ). The total content of sulfonate anion groups (—SO ₃ ⁻ ) is preferably 0.001 to 10% based on the weight of (a). The lower limit is more preferably 0.002%, and the upper limit is more preferably 5%, particularly preferably 2%, and most preferably 1%. Further, a sulfonic acid anion group to form the resin (-SO ₃ ^-) preferred carbon number of the monomer containing 3 to 50, more preferably 3 to 30, particularly preferably from 4 to 15.
When the sulfonate anion group (—SO ₃ ⁻ ) group content is not less than the lower limit of the above range and the carbon number of the monomer containing the sulfonate anion group (—SO ₃ ⁻ ) forming the resin is not more than the upper limit of the above range. The resin (a) is easily dispersed in an aqueous medium, and an aqueous dispersion (W) of fine spherical resin particles (A) can be easily obtained. Moreover, the blocking resistance and charging characteristics of the resulting resin particles (D) are improved.

Hereinafter, vinyl resin, polyester resin, polyurethane resin, and epoxy resin which are preferable resins as (a) will be described in detail.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer include the following (1) to (10).

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

(2) Carboxyl group-containing vinyl monomer and metal salt thereof:
C3-C30 unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and anhydrides thereof and monoalkyl (C1-24) esters thereof such as (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxylic group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid.
In addition, the said (meth) acrylic acid means acrylic acid and / or methacrylic acid, and the same description method is used hereafter.

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

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

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

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

(In the formula, R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different, and when they are different, they may be random or block. Ar represents a benzene ring, n represents an integer of 1 to 50, and R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom.

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

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

(5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, etc.

(6) Nitrogen-containing vinyl monomer:
(6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, ( (Meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N- Arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, salts thereof, etc. (6-2) Amido group Vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc. (6-3) Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene (6-4) quaternary ammonium cation group-containing vinyl monomers: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethyl Aminoethyl (meth) acrylamide, quaternized product of tertiary amine group-containing vinyl monomers such as diallylamine (methyl chloride, dimethyl sulfate, benzyl chloride, which was quaternized with quaternizing agents such as dimethyl carbonate)
(6-5) Nitro group-containing vinyl monomer: nitrostyrene, etc.

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

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

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl butyrate, vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl ( (Meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxyacrylate, alkyl (meth) acrylate having 1 to 50 carbon atoms (straight or branched) (preferably having 5 to 30 carbon atoms) [methyl ( (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate , Hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, 2-decyltetradecyl (meth) acrylate, etc.], dialkyl fumarate (dialkyl fumarate ester) (two alkyl groups have carbon number 2-8, linear, branched or alicyclic groups), dialkyl maleates (dialkyl maleates) (2 alkyl groups are straight chain, branched, 2-8 carbon atoms) Is a chain or alicyclic group), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane Etc.] and other vinyl monomers having a polyalkylene glycol chain [polyethylene glycol ( Molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylate, methyl alcohol ethylene oxide (ethylene oxide is abbreviated as EO hereinafter) 10 mole adduct (meth) acrylate, lauryl alcohol EO 30 mole adduct (meth) Acrylates, etc.], poly (meth) acrylates [poly (meth) acrylates of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.] etc. (9-2) Vinyl (thio) ether such as vinyl methyl ether, vinyl ethyl ether, vinyl Pyrether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro1,2-pyran, 2-butoxy-2 ′ -Vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, etc. (9-3) Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone;
Vinyl sulfones, such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, etc.

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

As the vinyl resin, the arbitrary monomers of the above (1) to (10) are binary or more, preferably the carboxyl group content in the resin particles (A) is 1 to 50%. Polymers copolymerized at an arbitrary ratio include vinyl acetate, (meth) acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, maleic acid dialkyl ester, and fumaric acid. , One or more selected from monoalkyl esters of fumaric acid, dialkyl esters of fumaric acid, alkyl (meth) acrylates having 5 to 27 carbon atoms, and aliphatic vinyl hydrocarbons having 2 to 4 carbon atoms are preferable. More preferably, it is at least one monomer selected from (meth) acrylic acid, vinyl acetate, alkyl (meth) acrylate having 5 to 27 carbon atoms having a branched structure, and aliphatic vinyl hydrocarbon having 2 to 4 carbon atoms. is there.
Specific examples of the copolymerized polymer include styrene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene-butadiene- (meth) acrylic acid copolymer, (meth) acrylic acid-acrylic acid ester. Copolymer, styrene-acrylonitrile- (meth) acrylic acid-divinylbenzene copolymer, styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid alkyl ester- (meth) acrylic Acid-alkylallylsulfosuccinate copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-crotonic acid- (meth) acrylic acid ester copolymer, vinyl acetate- (meth) acrylic acid copolymer, vinyl acetate -(Meth) acrylic acid ester copolymer, vinyl acetate- (meth) acrylic acid- (meth) Crylate ester copolymer, vinyl acetate-maleic anhydride copolymer, vinyl acetate-maleic anhydride- (meth) acrylic acid alkyl ester copolymer, vinyl acetate- (meth) acrylic acid-alkyl (meth) acrylate- Perfluoroalkyl (alkyl) (meth) acrylate copolymer, vinyl acetate-maleic anhydride- (meth) acrylic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-ethylene- (meth) acrylic acid copolymer Polymer, vinyl acetate-ethylene- (meth) acrylic acid alkyl ester copolymer, vinyl acetate-maleic anhydride- (meth) acrylic acid alkyl ester- (meth) acryloyloxypolyoxyalkylene sulfate copolymer, acetic acid Vinyl- (meth) acrylic acid-alkyl (meth) acrylate-perfluo Alkyl (alkyl) (meth) acrylate - alkyl allyl sulfosuccinate copolymer, and the like salts of these copolymers.

  In addition, when the resin (a) forms the resin particles (A) in the aqueous dispersion (X1), it is necessary that the resin (a) is not completely dissolved in water at least under the conditions for forming (X1). Therefore, although the ratio of the hydrophobic monomer and the hydrophilic monomer constituting the vinyl resin depends on the type of monomer selected, generally the hydrophobic monomer is preferably 20% or more, and more preferably 30% or more. When the ratio of the hydrophobic monomer is less than 10%, the vinyl resin becomes water-soluble, and the particle size uniformity of the resin particles (C) and (D) may be impaired. Here, the hydrophilic monomer means a monomer that dissolves in water at an arbitrary ratio, and the hydrophobic monomer means another monomer (a monomer that is basically not miscible with water).

Examples of polyester resins include polycondensates of polyols with polycarboxylic acids or acid anhydrides or lower alkyl esters thereof, and metal salts of these polycondensates. The polyol is a diol (11) and a polyol having a valence of 3 to 8 or more (12), and the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (13) and a valence of 3 to 6 or more. The above polycarboxylic acid (14) and these acid anhydrides or lower alkyl esters are mentioned.
The reaction ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/5, more preferably 1.5 / 1, as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. ˜¼, particularly preferably from 1 / 1.3 to ３.
In order to keep the carboxyl group content within the above preferred range, the polyester having an excess of hydroxyl groups may be treated with polycarboxylic acid.

  Examples of the diol (11) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, Decanediol, dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol) , Polypropylene glycol, polytetramethylene ether glycol, etc.); C4-C36 alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); Alkylene oxide (hereinafter abbreviated as AO) of recall or alicyclic diol [EO, propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] adducts (addition mole number 1 to 120) Bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) AO (EO, PO, BO, etc.) adducts (addition mole number 2-30); polylactone diol (poly ε-caprolactone diol, etc.); and polybutadiene diol Etc.

As the diol, in addition to the diol having no functional group other than the hydroxyl group, a diol (11a) having another functional group may be used. Examples of (11a) include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Diols having a carboxyl group include dialkylol alkanoic acids [things of C6-24, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid. 2,2-dimethylol octanoic acid, etc.].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, sulfoisophthalic acid di (ethylene glycol) ester, sulfamic acid diol [N, N-bis ( 2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) or an AO adduct thereof (AO includes EO or PO, AO addition mole number 1-6): for example, N, N-bis (2-hydroxyethyl) ) Sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adducts and the like]; bis (2-hydroxyethyl) phosphate and the like.
Examples of the neutralizing base of the diol having these neutralizing bases include the tertiary amines having 3 to 30 carbon atoms (such as triethylamine) and / or alkali metals (such as sodium salts).
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof.

Examples of the polyol (12) having 3 to 8 or more valences include 3 to 8 or more polyhydric aliphatic alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates thereof such as glycerin, Trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerol; saccharides and derivatives thereof such as sucrose and methylglucoside); AO adducts of polyhydric aliphatic alcohols (addition mole number: 2-120) AO adducts of trisphenols (such as trisphenol PA) (addition mole number 2 to 30); AO adducts (nomoles of phenol novolak, cresol novolak, etc.) (addition mole number 2 to 30); acrylic polyol [hydroxy Ethyl (meth) acrylate and others Such as copolymer of vinyl monomers]; and the like.
Among these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts, and more preferred are novolak resin AO adducts.

Examples of the dicarboxylic acid (13) include alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.) and alkenyl succinic acids (dodecenyl succinic acid, Pentadecenyl succinic acid, octadecenyl succinic acid, etc.); alicyclic dicarboxylic acid having 6 to 40 carbon atoms [dimer acid (dimerized linoleic acid), etc.], alkenedicarboxylic acid having 4 to 36 carbon atoms (maleic acid) Acid, fumaric acid, citraconic acid, etc.); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
Examples of the tricarboxylic acid having a valence of 3 to 6 or more (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
As the dicarboxylic acid (13) or the polycarboxylic acid (14) having 3 to 6 or more valences, the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester) Etc.) may be used.

The polyester resin used in the present invention may be produced in the same manner as a normal polyester production method. For example, the reaction temperature is preferably 150 to 280 ° C. and the reaction time is preferably 30 minutes or longer in an inert gas (nitrogen gas or the like) atmosphere.
At this time, an esterification catalyst can be used as needed. Examples of the esterification catalyst include a tin-containing catalyst (for example, dibutyltin oxide), antimony trioxide, and a titanium-containing catalyst [for example, titanium alkoxide, potassium oxalate titanate, titanium terephthalate, a catalyst described in JP-A-2006-243715. (Titanium dihydroxybis (triethanolamate), titanium monohydroxytris (triethanolamate), and intramolecular polycondensates thereof), and catalysts described in JP-A No. 2007-11307 (titanium tributoxyterephthalate) , Titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.)], zirconium-containing catalyst (for example, zirconyl acetate), zinc acetate and the like. Among these, preferred is a titanium-containing catalyst from the viewpoint of charging characteristics of the resin particles (D), and more preferred is a catalyst described in JP-A-2006-243715, and JP-A-2007-11307. The catalyst described.

  As the polyurethane resin, polyisocyanate (15) and active hydrogen-containing compound {water, polyol [diol (11) [including diol (11a) having a functional group other than hydroxyl group], and 3 to 8 or more valences] Polyol (12)], polycarboxylic acid [dicarboxylic acid (13), and polycarboxylic acid (14) having 3 to 6 or more valences], polyester polyol obtained by polycondensation of polyol and polycarboxylic acid, carbon number 6 -12 ring-opening polymer of lactone, polyamine (16), polythiol (17), and a polyaddition of these, etc.}, and a terminal isocyanate group prepolymer obtained by reacting (15) with an active hydrogen-containing compound And an equal amount of primary and / or secondary monoamines relative to the isocyanate groups of the prepolymer 18) 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%.

  Examples of the diol (11), 3 to 8 or more polyol (12), dicarboxylic acid (13), and 3 to 6 or more polycarboxylic acid (14) include those described above, and are preferable. The thing is the same.

  As polyisocyanate (15), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 alicyclic (excluding carbon in NCO group, the same shall apply hereinafter) Formula polyisocyanates, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, Oxazolidone group-containing modified products) and mixtures of two or more thereof.

Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4 ′. -And / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with an aromatic amine (aniline) or mixtures thereof; diaminodiphenylmethane and minor amounts (eg 5-20%] )) With a trifunctional or higher polyamine]: Polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- and p -Isocyanatophenylsulfonyl isocyanate Etc., and the like.
Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate And aliphatic polyisocyanates.
Specific examples of the alicyclic polyisocyanate 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- and / or 2,6-norbornane diisocyanate.
Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.
Examples of the modified polyisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified polyisocyanates such as urethane-modified TDI, and mixtures of two or more of these [for example, modified MDI and urethane-modified TDI (Use in combination with an isocyanate-containing prepolymer)].
Of these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

Examples of polyamine (16) include aliphatic polyamines (C2 to C18): [1] Aliphatic polyamine {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) , Polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; [2] these alkyls (C1-C4 ) Or substituted hydroxyalkyl (C2-C4) [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexa Methylenediamine, methyliminobispropylamine, etc.]; [3] Alicyclic or heterocyclic aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5, 5] Undecane etc.]; [4] Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine etc.), alicyclic polyamines (C4 to C15): 1,3- Heterocyclic polyamines (C4-C15) such as diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline): piperazine, N-aminoethylpiperazine, 1,4- Aromatics such as diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine Reamines (C6-C20): [1] Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethane Diamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ', 4 "-triamine, naphthylenediamine, etc .; [2] aromatic polyamines having a nucleus-substituted alkyl group (C1-C4 alkyl groups such as methyl, ethyl, n- and i-propyl, butyl, etc.), for example 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylene Diamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2, , 3-Dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetra Methyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,3′-diethyl-2,2′-diame Diphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl-4 , 4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone, etc.], and mixtures of these isomers in various proportions; [3] nuclear substitution electron withdrawing Aromatic polyamines having groups (halogens such as Cl, Br, I, F; alkoxy groups such as methoxy and ethoxy; nitro groups, etc.) [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro -1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro -1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4′-diamino-3,3′-dimethyl-5,5′-dibromo-diphenylmethane 3,3′-dichlorobenzidine, 3,3′-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) ) Sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3) -Methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4'-methylenebis (2-bromoaniline), 4,4'-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; [4] Aromatic polyamines having secondary amino groups [above [1] to [1] A part or all of —NH ₂ of the aromatic polyamine of [3] is replaced by —NH—R ′ (R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4 ′ -Di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.], polyamide polyamines: dicarboxylic acids (such as dimer acids) and excess (more than 2 moles per mole of acid) polyamines ( Low molecular weight polyamide polyamines obtained by condensation with the above-mentioned alkylene diamines, polyalkylene polyamines, etc.) Polyether polyamines: polyethers Examples thereof include hydrides of cyanoethylated polyols (such as polyalkylene glycols).

Examples of the polythiol (17) include alkanedithiols having 2 to 36 carbon atoms (ethylene dithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.).
Examples of the primary and / or secondary monoamine (18) include alkylamines having 2 to 24 carbon atoms (such as ethylamine, n-butylamine, and isobutylamine).

  Examples of the epoxy resin include a ring-opening polymer of polyepoxide (19), polyepoxide (19) and active hydrogen group-containing compound (T) {water, polyol [the diol (11) and a polyol having 3 to 8 or more valences (12). ], The dicarboxylic acid (13), the tri- or hexavalent or higher polycarboxylic acid (14), the polyamine (16), the polythiol (17) and the like}, or the polyepoxide (19) And a cured product of dicarboxylic acid (13) or an acid anhydride of polycarboxylic acid (14) having 3 to 6 or more valences.

  The polyepoxide (19) used for this invention will not be specifically limited if it has two or more epoxy groups in a molecule | numerator. A thing preferable as a polyepoxide (19) has 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material. The epoxy equivalent of the polyepoxide (19) (molecular weight per epoxy group) is preferably 65 to 1000, and more preferably 90 to 500. When the epoxy equivalent is 1000 or less, the cross-linked structure becomes strong, and physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are improved. On the other hand, it is difficult to synthesize an epoxy equivalent of less than 65.

  Examples of the polyepoxide (19) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols. Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl di Glycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, Of glycol ether of enolic or cresol novolac resin, glycidyl ether of limonene phenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained by condensation reactions, polyglycidyl ethers of polyphenols obtained by condensation reactions of resorcin and acetone, and the like. Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate. Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like. Furthermore, in the present invention, the aromatic system is obtained by reacting a polyol with the above-mentioned two reactants, such as triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol. The glycidyl group-containing polyurethane (pre) polymer and an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A are also included. Heterocyclic polyepoxy compounds include trisglycidyl melamine; alicyclic polyepoxy compounds include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl). Ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexyl) Methyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester, and the like. The alicyclic group also includes a hydrogenated product of the aromatic polyepoxide compound; examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyvalent aliphatic alcohols and polyglycidyl esters of polyvalent fatty acids. Body, and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether It is done. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. In the present invention, the aliphatic type also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more polyepoxides may be used in combination.

In the production method of the present invention, an aqueous dispersion (W) containing the resin particles (A) comprising the first resin (a) and the flocculant (E), the resin (b) or an organic solvent solution thereof, or Resin (b) precursor (b0) or its organic solvent solution (O) is mixed and (O) is dispersed in (W) to form resin particles (B) comprising (b). In this case, the resin particles (A) are adsorbed on the surface of the resin particles (B) to prevent the resin particles (C) from being united with each other, and the (C) is hardly split under high shear conditions. . Thereby, the particle diameter of (C) is converged to a constant value, and the effect of improving the uniformity of the particle diameter is exhibited. Therefore, the resin particles (A) have a strength not to be destroyed by shearing at the temperature at the time of dispersion, are not easily dissolved or swelled in water, (b) or an organic solvent solution thereof, or As a preferable characteristic, it is difficult to dissolve in (b0) or the organic solvent solution (O) thereof.
Among (b) and (b0), from the viewpoint of productivity, a method using (b) or an organic solvent solution thereof is preferable.

In the above production method, by incorporating the flocculant (E) in the aqueous dispersion (X1), the effect of increasing the particle size uniformity by converging the particle size of (C) to a more constant value. Demonstrate. If the content of the flocculant (E) at this time is 0.001% or more, the agglomeration effect is expressed and the uniformity of the particle diameter can be improved. If it is 20% or less, the resin particles (C) are combined. It becomes difficult to do. When the content of the flocculant (E) in (X1) is 0.1 to 15%, the uniformity of the particles can be further increased, and it is more preferable.
Moreover, the shape of (C) is controllable by containing a flocculant (E). When the content of the flocculant (E) is large, the shape can be more distorted, and when the content of the flocculant (E) is small, the shape becomes more spherical.

Examples of the flocculant (E) used here include inorganic acid metal salts (preferably alkali metal salts, alkaline earth metal salts, and aluminum salts), and two or more kinds may be used in combination.
Examples of the alkali metal constituting the salt include lithium, potassium, sodium, etc., examples of the alkaline earth metal include magnesium, calcium, strontium, barium and the like, and other metals such as trivalent or higher aluminum. Metals can also be used. Preferred are potassium, sodium, magnesium, calcium, barium, and aluminum. Examples of the inorganic acid constituting the salt include hydrochloric acid, hydrobromic acid, hydroiodic acid, carbonic acid, sulfuric acid and the like, preferably hydrochloric acid and sulfuric acid. Specific examples include sodium chloride, potassium chloride, calcium chloride, magnesium sulfate, aluminum chloride and the like.

  From the viewpoint of reducing the dissolution or swelling of the resin particles (A) in water or an organic solvent used for dispersion, the molecular weight of the resin (a), the sp value (the calculation method of the sp value is Polymer Engineering). and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154), the melting point and the like are preferably adjusted as appropriate.

  The number average molecular weight (measured by gel permeation chromatography, hereinafter abbreviated as Mn) of the resin (a) is preferably from 1 to 5 million, more preferably from 2 to 5 million, particularly preferably from 500 to 500,000. , Sp value is preferably 7-18, more preferably 8-14. The melting point (measured by DSC) of the resin (a) is preferably 50 ° C. or higher, more preferably 80 to 200 ° C.

In the present invention, the Mn of a resin other than polyurethane (polyester resin or the like) and the weight average molecular weight (hereinafter abbreviated as Mw) are as follows using a gel permeation chromatography (GPC) for tetrahydrofuran (THF) soluble matter. Measured in
Device (example): Tosoh HLC-8120
Column (example): TSKgelGMHXL (2)
TSKgelMultiporeHXL-M (1 pc.)
Sample solution: 0.25% THF solution Injection volume: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detection apparatus: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSYRENE) manufactured by Tosoh (molecular weight 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000 4480000)

Moreover, Mn and Mw of a polyurethane resin are measured on condition of the following using GPC.
Equipment (example): Tosoh HLC-8220GPC
Column (example): Guardcolumn α
TSKgel α-M
Sample solution: 0.125% dimethylformamide solution Solution injection amount: 100 μl
Flow rate: 1 ml / min Temperature: 40 ° C
Detection apparatus: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

The glass transition temperature (Tg) of the resin (a) is preferably 20 ° C. to 250 ° C. from the viewpoints of the particle size uniformity of the resin particles (D), powder flowability, heat resistance during storage, and stress resistance. More preferably, it is 30 degreeC-230 degreeC, More preferably, it is 40 degreeC-200 degreeC, Most preferably, it is 50 degreeC-120 degreeC. If the Tg is higher than the temperature at which the aqueous dispersion (X1) is produced, the effect of preventing coalescence or preventing splitting is increased, and the effect of increasing the uniformity of particle size is increased.
The Tg of the resin particles (A) comprising (a) or the coating (P) of the resin (a) is preferably 20 to 200 ° C., more preferably 30 to 100 ° C., and particularly preferably 40 for the same reason. ~ 85 ° C.
In addition, Tg in this invention is a value calculated | required from DSC measurement or a flow tester measurement (when it cannot measure by DSC).

In the case of measurement by DSC, it is measured by a method (DSC method) prescribed in ASTM D3418-82 using DSC20 and SSC / 580 manufactured by Seiko Electronics Industry.
For the flow tester measurement, an elevated flow tester CFT500 type manufactured by Shimadzu Corporation is used. The conditions for the flow tester measurement are as follows, and the following measurements are all performed under these conditions.
(Flow tester measurement conditions)
Load: 30 kg / cm ² , temperature rising rate: 3.0 ° C./min,
Die diameter: 0.50 mm, Die length: 10.0 mm

  Also, point A (the temperature at which the sample begins to deform under compression load) in the flowchart shown in FIG. 2 is the glass transition temperature (Tg), and point B (the internal void disappears and the appearance is maintained with a non-uniform stress distribution. The temperature at the uniform single transparent body or phase becomes the softening start temperature (Ts), point C (the piston slightly rises due to the thermal expansion of the sample, and then the piston clearly starts to fall again) The temperature at the point) is the outflow start temperature (Tfb), and the temperature at the point D (the point where the difference between the outflow end point Smax and the minimum value Smin is 1/2 (X) and X and Smin are added) Temperature (T1 / 2).

  The softening start temperature (Ts) of the resin (a) is preferably 40 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C., from the viewpoint of heat resistance during storage, stress resistance, and fixing properties to the paper surface. Particularly preferably, it is 60 ° C to 220 ° C, most preferably 70 ° C to 160 ° C, and the outflow temperature (T1 / 2) is preferably 60 ° C to 300 ° C, more preferably 65 ° C to 280 ° C, and particularly preferably 70 ° C. C. to 250.degree. C., most preferably 80.degree. C. to 180.degree. When used as toner or the like, the lower the softening start temperature (Ts) and the outflow temperature (T1 / 2), the more difficult it is to inhibit low-temperature fixability and high glossiness. In addition, the softening start temperature and outflow temperature in this invention are the values calculated | required from the said flow tester measurement.

The temperature difference between the glass transition temperature (Tg) and the outflow temperature (T1 / 2) of the resin (a) is preferably 0 ° C to 130 ° C, more preferably 0 ° C to 120 ° C, and particularly preferably 0 ° C to 100 ° C. Most preferably, it is 0 to 80 ° C. When the temperature difference between the glass transition temperature and the softening start temperature is within the above range, when the resin particles are used as a toner, it is easy to achieve both heat resistant storage of the resin particles and high gloss.
Moreover, the preferable temperature difference of the glass transition temperature (Tg) and softening start temperature (Ts) of resin (a) is 0 degreeC-100 degreeC, More preferably, it is 0 degreeC-70 degreeC, More preferably, it is 0 degreeC-50 degreeC. Especially preferably, it is 0 degreeC-35 degreeC. When the temperature difference between the glass transition temperature and the softening start temperature is within the above range, when the resin particles are used as a toner, it is easy to achieve both heat resistant storage of the resin particles and high gloss.

  The resin (a) is selected from the known resins as described above, and the glass transition temperature (Tg), the softening start temperature (Ts), and the outflow temperature (T1 / 2) of the resin (a) are adjusted. The molecular weight of (a) and / or the monomer composition constituting (a) can be easily adjusted. As a method for adjusting the molecular weight of (a) (the higher the molecular weight, these temperatures are higher), a known method may be used. For example, when polymerization is performed by a sequential reaction such as a polyurethane resin or a polyester resin. In the case of polymerizing by a chain reaction such as vinyl resin, adjustment of the polymerization initiator amount and chain transfer agent amount, reaction temperature, and reaction concentration can be mentioned. In order to adjust the temperature difference between the glass transition temperature (Tg) and the outflow temperature (T1 / 2), a combination of the molecular weight of (a) and the monomer composition constituting (a) may be appropriately selected. .

In the production method of the present invention, the resin particles (D) separate and remove and / or dissolve at least part of the resin particles (A) made of the resin (a) attached to the surface or the coating (P) of the resin (a). The resin (a), which cannot be completely removed but remains on the surface, has a softening start temperature (Ts), an outflow temperature (T1 / 2) and a glass transition temperature (Tg) within the above ranges. For example, when used for toner, low-temperature fixability and high glossiness may be improved.
The resin (a) used in the present invention has a softening start temperature of 40 to 270 ° C, a glass transition temperature of 20 to 250 ° C, an outflow temperature of 60 to 300 ° C, and a difference between the glass transition temperature of 0 to 130 ° C and the outflow temperature. It is preferable that it is resin which has all.

  In the aqueous dispersion (W) of the resin particles (A), a solvent miscible with water (acetone, methanol, methyl ethyl ketone, etc.) may be contained in the organic solvent (u) described later in addition to water. At this time, if the organic solvent contained does not cause aggregation of the resin particles (A), does not dissolve the resin particles (A), and does not interfere with granulation of the resin particles (C) Any kind and any content may be used, but it is preferable to use 40% or less of the total amount with water and not to remain in the resin particles (D) after drying.

Although the method to make resin (a) the aqueous dispersion (W) of resin particle (A) is not specifically limited, the following [1]-[8] are mentioned.
[1] In the case of vinyl resin, an aqueous dispersion of resin particles (A) is directly produced by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method using a monomer as a starting material. In the case of polyaddition or condensation resin such as polyester resin, the precursor (monomer, oligomer, etc.) or its organic solvent solution is dispersed in an aqueous medium in the presence of a suitable dispersant if necessary. In the case of polyaddition or condensation resin such as polyester resin, a method of producing an aqueous dispersion of resin particles (A) by subsequently heating or adding a curing agent to cure the precursor body, After an appropriate emulsifier is dissolved in a precursor (monomer, oligomer, etc.) or an organic solvent solution thereof (preferably in a liquid form, which may be liquefied by heating), if necessary. A method for producing an aqueous dispersion of resin particles (A) by adding water, emulsifying phase inversion emulsification, and adding a curing agent, etc. [4] Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization in advance) The polymerization reaction mode may be any of addition, addition condensation, condensation polymerization, etc. The same applies hereinafter.) The resin prepared by mechanical rotation type or jet type fine pulverizer is used and then classified. [5] A method of dispersing resin particles in water in the presence of an appropriate dispersing agent if necessary [5] Resin particles prepared by spraying a resin solution prepared by previously polymerizing reaction in an organic solvent in the form of a mist After the resin particles are obtained, a method of dispersing the resin particles in water in the presence of an appropriate dispersant as necessary [6] A poor solvent is added to a resin solution prepared by previously dissolving a resin prepared by a polymerization reaction in an organic solvent, or By precipitating resin particles by cooling the resin solution heated and dissolved in advance in an organic solvent, and then removing the organic solvent to obtain resin particles, the resin particles are placed in water in the presence of an appropriate dispersant if necessary. Dispersion method [7] A resin solution in which a resin prepared in advance by a polymerization reaction is dissolved in an organic solvent is dispersed in an aqueous medium in the presence of an appropriate dispersant as necessary, and the organic solvent is removed by heating or decompression. Method [8] A method in which a suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin prepared by a polymerization reaction in an organic solvent, and then water is added to perform phase inversion emulsification. Are the methods [1], [7] and [8].

In the above methods [1] to [8], as the emulsifier or dispersant used in combination, a known surfactant (s), water-soluble polymer (t) and the like can be used. Moreover, an organic solvent (u), a plasticizer (v), etc. can be used together as an auxiliary agent for emulsification or dispersion. However, the surfactant (s) contained in the aqueous dispersion (X1) of the resin particles (C) is preferably 1000 ppm or less, more preferably 100 ppm or less, and particularly preferably 40 ppm or less. It is preferable that the surfactant (s) to be used is in the above-mentioned range because the cleaning of (s) from the resin particles (D) is easy or unnecessary, and the obtained charging characteristics of (D) are improved. Incidentally, the content (%) of (s) is an amount (%) calculated from the raw material charge used for the production of (X1).
In the production method of the present invention, by using the flocculant (E), the aqueous dispersion (W) and the aqueous dispersion (X1) can be easily produced without using the surfactant (s).

  It does not specifically limit as surfactant (s), Anionic surfactant (s-1), Cationic surfactant (s-2), Amphoteric surfactant (s-3), Nonionic surfactant ( s-4). The surfactant (s) may be a combination of two or more surfactants. Specific examples of (s) include those described in JP-A-2002-284881 in addition to those described below.

  As the anionic surfactant (s-1), a carboxylic acid or a salt thereof, a sulfate ester salt, a salt of a carboxymethylated product, a sulfonate salt, a phosphate ester salt, or the like is used.

  As the cationic surfactant (s-2), a quaternary ammonium salt type surfactant, an amine salt type surfactant and the like can be used.

  Examples of the amphoteric surfactant (s-3) include a carboxylate type amphoteric surfactant, a sulfate ester type amphoteric surfactant, a sulfonate type amphoteric surfactant, and a phosphate ester type amphoteric surfactant. Can be used.

  As the nonionic surfactant (s-4), an alkylene oxide addition type nonionic surfactant and a polyvalent alcohol type nonionic surfactant can be used.

  Examples of the water-soluble polymer (t) include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin , Chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, in the sodium hydroxide part of polyacrylic acid) Sodium hydroxide, acrylic acid ester copolymer), styrene-maleic anhydride copolymer sodium hydroxide Beam (partial) neutralization product, water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.

The organic solvent (u) used in the present invention may be added to an aqueous medium as needed during emulsification and dispersion in the emulsified dispersion [in the oil phase (O) containing the resin (b) or (b0). ] May be added.
Specific examples of the organic solvent (u) include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit and cyclohexane. Solvents: Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, etc. Ester or ester ether solvents; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone, di-n-butyl ketone and cyclohexanone; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol; Examples include amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methylpyrrolidone; and mixed solvents of two or more of these.

The plasticizer (v) may be added to an aqueous medium as needed during the emulsification dispersion, or may be added to the emulsified dispersion [in the oil phase (O) containing the resin (b) or (b0)]. Also good.
As a plasticizer (v), it is not limited at all, The following are illustrated.
(V1) Phthalates [dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, etc.];
(V2) Aliphatic dibasic acid ester [di-2-ethylhexyl adipate, 2-ethylhexyl sebacate, etc.];
(V3) trimellitic acid ester [tri-2-ethylhexyl trimellitic acid, trioctyl trimellitic acid, etc.];
(V4) Phosphate ester [triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.];
(V5) fatty acid ester [butyl oleate and the like];
(V6) and a mixture of two or more of these.

  The particle size of the resin particles (A) used in the present invention is usually smaller than the particle size of the formed resin particles (B). From the viewpoint of particle size uniformity, the particle size ratio [volume of the resin particles (A) The value of [average particle diameter] / [volume average particle diameter of resin particles (B)] is preferably in the range of 0.001 to 0.3. The lower limit of the particle size ratio is more preferably 0.003, and the upper limit is more preferably 0.25. When the particle size ratio is smaller than 0.3, (A) is efficiently adsorbed on the surface of (B), and the uniformity of the resulting resin particles (C) and (D) tends to be high.

The volume average particle diameter of the resin particles (A) can be appropriately adjusted within the above range of particle diameter ratios so as to have a particle diameter suitable for obtaining the resin particles (D) having a desired particle diameter.
The volume average particle size of (A) is generally preferably 0.0005 to 30 μm. The upper limit is more preferably 20 μm, particularly preferably 10 μm, and the lower limit is further preferably 0.01 μm, particularly preferably 0.02 μm, and most preferably 0.04 μm. However, for example, when it is desired to obtain a resin particle (D) having a volume average particle diameter of 1 μm, it is preferably 0.0005 to 0.3 μm, particularly preferably in the range of 0.001 to 0.2 μm, and 10 μm resin particles ( In the case of obtaining D), preferably 0.005 to 3 μm, particularly preferably 0.05 to 2 μm, and 100 μm of particles (D) are preferably 0.05 to 30 μm, particularly preferably. 0.1 to 20 μm.
The volume average particle size is determined by laser type particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.), Multisizer III (manufactured by Coulter), ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) using the laser Doppler method as an optical system, and the like. Can be measured. If there is a difference in the measured particle size between the measuring devices, the measured value of ELS-800 is adopted.
In addition, since the said particle size ratio is easy to be obtained, 0.1-300 micrometers is preferable as the volume average particle diameter of the resin particle (B) mentioned later. More preferably, it is 0.5-250 micrometers, Most preferably, it is 1-200 micrometers.

As the second resin (b) of the present invention, any resin can be used as long as it is a known resin, and specific examples thereof can be the same as those of the resin (a). (B) can select a preferable thing suitably according to a use and the objective.
In general, the resin (b) is preferably a vinyl resin, a polyester resin, a polyurethane resin, an epoxy resin, and a combination thereof, and more preferably a polyurethane resin and a polyester resin.

The Mn, melting point, Tg, and sp value of the resin (b) may be appropriately adjusted within a preferable range depending on the application.
The sp value of the resin (b) is preferably 7 to 18, more preferably 8 to 14, and particularly preferably 9 to 14.
For example, when the resin particles (D) are used as a slush molding resin or a powder coating, the Mn of (b) is preferably 2,000 to 500,000, more preferably 4,000 to 200,000. The melting point (measured by DSC, hereinafter the melting point is a measured value by DSC) of (b) is preferably 0 ° C to 200 ° C, more preferably 35 ° C to 150 ° C. The Tg of (b) is preferably −60 ° C. to 100 ° C., more preferably −30 ° C. to 60 ° C.
When used as a spacer for manufacturing electronic parts such as liquid crystal displays and standard particles for electronic measuring instruments, the Mn of (b) is preferably 20,000 to 10,000,000, more preferably 40,000 to 2,000,000. The melting point of (b) is preferably 40 ° C to 300 ° C, more preferably 70 ° C to 250 ° C. The Tg of (b) is preferably −0 ° C. to 250 ° C., more preferably 50 ° C. to 200 ° C.
When used as a toner used for electrophotography, electrostatic recording, electrostatic printing, etc., the Mn of (b) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000. The melting point of (b) is preferably 20 ° C to 300 ° C, more preferably 80 ° C to 250 ° C. The Tg of (b) is preferably 20 ° C to 200 ° C, more preferably 40 ° C to 150 ° C. The sp value of (b) is preferably 8-16, more preferably 9-14.

In the production method of the present invention, the aqueous dispersion (W) containing the resin particles (A) comprising the first resin (a) and the flocculant (E), the second resin (b) or an organic solvent thereof The resin particles (B) are formed by mixing the solution and dispersing (b) or an organic solvent solution thereof in (W) to form resin particles (B) comprising (b) in (W). After obtaining an aqueous dispersion (X1) of the resin particles (C) having a structure in which the resin particles (A) or the coating (P) of the resin (a) is attached to the surface of the resin, the resin on the surface of the resin particles (C) is obtained. At least a part of the particles (A) or the coating (P) is separated and / or dissolved and removed, and consists of (B), or a part of the surface of (B) is coated with (A) or (P) An aqueous dispersion (X2) of the obtained resin particles (D) is obtained.
Alternatively, the aqueous dispersion (W) containing the resin particles (A) made of the first resin (a) and the flocculant (E), the precursor (b0) of the second resin (b), or an organic solvent thereof The solution is mixed, (b0) or its organic solvent solution is dispersed in (W), and (b0) is further reacted to form resin particles (B) comprising (b) in (W). After obtaining the aqueous dispersion (X1) of the resin particles (C) having a structure in which the coating of the resin particles (A) or the resin (a) (P) is adhered to the surface of the resin particles (B), At least a part of the resin particles (A) or the coating (P) on the surface of the resin particles (C) is separated and / or dissolved and removed, and consists of (B), or a part of the surface of (B) is ( An aqueous dispersion (X2) of resin particles (D) coated with A) or (P) is obtained.
Note that (b) and (b0) may be used in combination.

When the resin (b) or an organic solvent solution thereof, or the precursor (b0) of the resin (b) or the organic solvent solution thereof is dispersed in the aqueous dispersion (W), a dispersing device can be used.
The dispersion apparatus used in the present invention is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. For example, a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer ( Batch type emulsifier such as Special Machine Industries Co., Ltd., Ebara Milder (Ebara Manufacturing Co., Ltd.), TK Fill Mix, TK Pipeline Homo Mixer (Special Machine Industries Co., Ltd.), Colloid Mill (Shinko Pantech Co., Ltd.) ), Continuous emulsifiers such as slasher, trigonal wet pulverizer (Mitsui Miike Chemical Co., Ltd.), Captron (Eurotech Co., Ltd.), fine flow mill (Pacific Kiko Co., Ltd.), microfluidizer (Mizuho Kogyo Co., Ltd.) ), Nanomizer (manufactured by Nanomizer), APV Gaurin (manufactured by Gaurin) Membrane emulsifier, Vibro Mixer (Hiyaka Kogyo) vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of homogenizing the particle diameter.

When the resin (b) is dispersed in the aqueous dispersion (W) of the resin particles (A), the resin (b) is preferably a liquid. When the resin (b) is solid at room temperature, it may be dispersed in a liquid state at a high temperature equal to or higher than the melting point, or the organic solvent solution (b) may be used.
The viscosity of the resin (b) or its organic solvent solution, or the precursor (b0) or its organic solvent solution is preferably 10 to 50,000 mPa · s (measured with a B-type viscometer from the viewpoint of particle size uniformity. ), More preferably 100 to 10,000 mPa · s.
The temperature during dispersion is preferably 0 to 150 ° C. (under pressure), more preferably 5 to 98 ° C. When the viscosity of the dispersion is high, it is preferable to carry out emulsification dispersion by raising the temperature and decreasing the viscosity to the above preferred range.
The organic solvent used for the organic solvent solution of the resin (b) or the precursor (b0) is not particularly limited as long as it is a solvent that can dissolve the resin (b) at room temperature or under heating. Specifically, the organic solvent ( The same thing as u) is illustrated. The preferred one varies depending on the type of the resin (b), but the sp value difference from (b) is preferably 3 or less. Moreover, from the viewpoint of the particle size uniformity of the resin particles (C), an organic solvent that dissolves the resin (b) but hardly dissolves and swells the resin particles (A) made of the resin (a) is preferable.

  The precursor (b0) of the resin (b) is not particularly limited as long as it can be converted into the resin (b) by a chemical reaction. For example, the resin (b) is a condensation resin (for example, polyurethane resin, epoxy resin). (B0) is a combination of a prepolymer (α) having a reactive group and a curing agent (β), and when the resin (b) is a vinyl resin, (b0) is And the above-mentioned vinyl monomers (which may be used alone or in combination) and organic solvent solutions thereof.

  When a vinyl monomer is used as the precursor (b0), the method of reacting the precursor (b0) to obtain a resin (b) includes, for example, an oil-soluble initiator, monomers, and, if necessary, an organic solvent (u). A method in which the oil phase is dispersed and suspended in the aqueous dispersion (W) of the resin particles (A) in the presence of the water-soluble polymer (t) and a radical polymerization reaction is carried out by heating (so-called suspension polymerization method), monomer An oil phase comprising an organic solvent (u) if necessary, an emulsifier (similar to the surfactant (s) is exemplified), and an aqueous dispersion (W) of resin particles (A) containing a water-soluble initiator Examples thereof include a method of emulsifying the solution therein and performing a radical polymerization reaction by heating (so-called emulsion polymerization method).

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

(I) As the peroxide polymerization initiator, (I-1) oil-soluble peroxide polymerization initiator: acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxy Dicarbonate, 2,4-dichlorobenzoyl peroxide, t-butyl peroxybivalate, octanoyl peroxide, lauroyl peroxide, propionitrile peroxide, succinic acid peroxide, acetyl peroxide, t-butyl peroxide 2-ethylhexanoate, benzoyl peroxide, parachlorobenzoyl peroxide, t-butyl peroxyisobutyrate, t-butyl peroxymaleic acid, t-butyl -Oxylaurate, cyclohexanone peroxide, t-butyl peroxyisopropyl carbonate, t-butyl peroxyacetate, t-butyl peroxybenzoate, diisobutyl diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl cumi Ruperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene peroxide, etc. (I -2) Water-soluble peroxide polymerization initiator: hydrogen peroxide, peracetic acid, ammonium persulfate, sodium persulfate, etc.

(II) Azo polymerization initiator:
(II-1) Oil-soluble azo polymerization initiator: 2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexane 1-carbonitrile, 2,2′-azobis-4-methoxy-2 , 4-dimethylvaleronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2′-azobis (2-methylpropionate), 1,1′-azobis (1-acetoxy- 1-phenylethane), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. (II-2) Water-soluble azo polymerization initiator: azobisamidinopropane salt, azobiscyanovaleric Acid (salt), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], etc.

(III) Redox polymerization initiator (III-1) Non-aqueous redox polymerization initiator: oil-soluble peroxide such as hydroperoxide, dialkyl peroxide, diacyl peroxide, tertiary amine, naphthenic acid salt, mercaptans In combination with oil-soluble reducing agents such as organometallic compounds (triethylaluminum, triethylboron, diethylzinc, etc.) (III-2) Water-based redox polymerization initiators: water-soluble such as persulfate, hydrogen peroxide, hydroperoxide Examples thereof include a combination of a peroxide and a water-soluble inorganic or organic reducing agent (divalent iron salt, sodium hydrogen sulfite, alcohol, polyamine, etc.).

  As the precursor (b0), a combination of a prepolymer (α) having a reactive group and a curing agent (β) can also be used. Here, “reactive group” means a group capable of reacting with the curing agent (β). In this case, as a method of forming the resin (b) by reacting the precursor (b0), an oil phase containing a reactive group-containing prepolymer (α), a curing agent (β) and, if necessary, an organic solvent (u) is used. Are dispersed in an aqueous dispersion (W) of resin particles (A), and resin particles (B) made of resin (b) in which a reactive group-containing prepolymer (α) and a curing agent (β) are reacted by heating. A reactive group-containing prepolymer (α) or an organic solvent solution thereof is dispersed in an aqueous dispersion (W) of resin particles (A), and a water-soluble curing agent (β) is added thereto. A method of reacting to form resin particles (B) comprising the resin (b); when the reactive group-containing prepolymer (α) is cured by reacting with water, the reactive group-containing prepolymer ( α) or an organic solvent solution thereof is used as an aqueous dispersion of resin particles (A) (W The method of making it react with water by making it disperse | distribute to (B) and forming the resin particle (B) which consists of (b) etc. can be illustrated.

Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (α) and the curing agent (β) include the following [1] and [2].
[1]: The reactive group of the reactive group-containing prepolymer (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and the curing agent (β) is an active hydrogen group-containing compound (β1). There is a combination.
[2]: The reactive group of the reactive group-containing prepolymer (α) is an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) that can react with the active hydrogen-containing group. combination.
Among these, [1] is more preferable from the viewpoint of the reaction rate in water.
In the combination [1], the functional group (α1) capable of reacting with the active hydrogen compound includes an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (α1d) and And acid halide groups (α1e). Among these, (α1a), (α1b) and (α1c) are preferable, and (α1a) and (α1b) are particularly preferable.
The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent.
Examples of the blocking agent include oximes [acetooxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; lactams [γ-butyrolactam, ε-caprolactam, γ-valerolactam Etc.]; C1-C20 aliphatic alcohols [ethanol, methanol, octanol, etc.]; Phenols [phenol, m-cresol, xylenol, nonylphenol, etc.]; Active methylene compounds [acetylacetone, ethyl malonate, ethyl acetoacetate, etc.] Etc.]; basic nitrogen-containing compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.]; and mixtures of two or more thereof That.
Of these, oximes are preferred, and methyl ethyl ketoxime is particularly preferred.

Examples of the skeleton of the reactive group-containing prepolymer (α) include polyether (αw), polyester (αx), epoxy resin (αy), and polyurethane (αz). Of these, (αx), (αy) and (αz) are preferred, and (αx) and (αz) are particularly preferred.
Examples of the polyether (αw) include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, and the like.
Examples of the polyester (αx) include a polycondensate of diol (11) and dicarboxylic acid (13), polylactone (a ring-opening polymerization product of ε-caprolactone), and the like.
Examples of the epoxy resin (αy) include addition condensation products of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S) and epichlorohydrin.
Examples of polyurethane (αz) include polyaddition product of diol (11) and polyisocyanate (15), polyaddition product of polyester (αx) and polyisocyanate (15), and the like.

As a method of adding a reactive group to polyester (αx), epoxy resin (αy), polyurethane (αz), etc.,
[1]: A method of leaving a functional group of a constituent component at the terminal by excessively using one of two or more constituent components,
[2]: The functional group of the constituent component is left at the terminal by using one of two or more constituent components in excess, and further contains a functional group and a reactive group capable of reacting with the remaining functional group. Examples include a method of reacting a compound.
In the above method [1], a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, an isocyanate A group-containing polyurethane prepolymer or the like is obtained.
For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is such that the ratio of polyol [diol (11), etc.] and polycarboxylic acid [dicarboxylic acid (13), etc.] is hydroxyl group [OH] and carboxyl group [COOH]. The equivalent ratio [OH] / [COOH] is preferably 2/1 to 1.01 / 1, more preferably 1.5 / 1 to 1.01 / 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 to cause a blocked isocyanate group-containing prepolymer. A polymer is obtained, an epoxy group-containing prepolymer is obtained by reacting polyepoxide, and an acid anhydride group-containing prepolymer is obtained by reacting polyanhydride.
The amount of the compound containing a functional group and a reactive group is, for example, when the isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate, 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 1.01 / 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 usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. By setting it as the above range, the molecular weight of the cured product obtained by reacting with the curing agent (β) is increased.
The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and most 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 2,000 poise or less, more preferably 1,000 poise or less at 100 ° C. By setting it to 2,000 poise or less, it is preferable in that resin particles (C) and (D) having a sharp particle size distribution can be obtained.

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

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

Examples of the polyol (β1b) are the same as the diol (11) and the trivalent to octavalent or higher polyol (12). Diol (11) alone or a mixture of diol (11) and a small amount of polyol (12) is preferred.
Examples of the polymercaptan (β1c) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

If necessary, a reaction terminator (βs) can be used together with the active hydrogen group-containing compound (β1). By using a reaction terminator in combination with (β1) at a certain ratio, it is possible to adjust (b) to a predetermined molecular weight.
As a reaction terminator (βs), monoamine (diethylamine, dibutylamine, butylamine, laurylamine, monoethanolamine, diethanolamine, etc.);
Monoamine blocked (such as ketimine compound);
Monools (methanol, ethanol, isopropanol, butanol, phenol, etc.);
Monomercaptan (such as butyl mercaptan, lauryl mercaptan);
Monoisocyanates (such as lauryl isocyanate, phenyl isocyanate);
Examples thereof include monoepoxide (such as butyl glycidyl ether).

As the active hydrogen-containing group (α2) of the reactive group-containing prepolymer (α) in the combination [2], an amino group (α2a), a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), a mercapto group ( α2c), a carboxyl group (α2d), and an organic group (α2e) blocked with a compound from which they can be removed. Of these, (α2a), (α2b) and an organic group (α2e) blocked with a compound capable of removing an amino group are preferred, and (α2b) is particularly preferred.
Examples of the organic group blocked with the compound from which the amino group can be removed include the same groups as in the case of (β1a).

  Examples of the compound (β2) capable of reacting with an active hydrogen-containing group include polyisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polyanhydride (β2d), and polyacid halide (β2e). It is done. Of these, (β2a) and (β2b) are preferable, and (β2a) is more preferable.

Examples of the polyisocyanate (β2a) include those similar to the polyisocyanate (15), and preferred ones are also the same.
Examples of the polyepoxide (β2b) are the same as those of the polyepoxide (19), and preferred ones are also the same.

Examples of the polycarboxylic acid (β2c) include dicarboxylic acid (β2c-1) and trivalent or higher polycarboxylic acid (β2c-2). (Β2c-1) alone and (β2c-1) and a small amount of ( A mixture of β2c-2) is preferred.
Examples of the dicarboxylic acid (β2c-1) are the same as the dicarboxylic acid (13) and the polycarboxylic acid (β2c-2) is the same as the polycarboxylic acid (14) having 3 to 6 or more valences. The preferred ones are also the same.

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

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

  Resin (b) obtained by reacting a precursor (b0) comprising a reactive group-containing prepolymer (α) and a curing agent (β) in an aqueous medium is a constituent of resin particles (B) and resin particles (C). Become. The Mw of the resin (b) obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) is preferably 3,000 or more, more preferably 3,000 to 10,000,000, particularly preferably 5,000 to 100. Ten thousand.

  In the aqueous dispersion (W), a polymer that does not react with the reactive group-containing prepolymer (α) and the curing agent (β) during the reaction of the reactive group-containing prepolymer (α) and the curing agent (β) [ A so-called dead polymer] can also be contained in the system. In this case, (b) is a mixture of a resin obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) in an aqueous medium and a resin not reacted (dead polymer).

  The amount of the aqueous dispersion (W) used with respect to 100 parts by weight of the resin (b) or the precursor (b0) is preferably 50 to 2,000 parts by weight, more preferably 100 to 1,000 parts by weight. If it is 50 parts by weight or more, the dispersed state of (b) is good, and if it is 2,000 parts by weight or less, it is economical.

In the present invention, the adsorption force of the resin particles (A) for obtaining the resin particles (C) to the resin particles (B) can be controlled by the following method.
[1]: When the aqueous dispersion (X1) is produced, if the resin (a) and the resin (b) are made to have positive and negative charges, an adsorption force is generated. In this case, the resin (a) and the resin (B) The greater the charge of each, the stronger the adsorption force, and the greater the coverage of the resin (a) with respect to the resin (b).
[2]: When the aqueous dispersion (X1) is produced, if the resin (a) and the resin (b) are charged with the same polarity (both positive or both negative), the coverage is lowered. There is a tendency. In this case, in general, when the surfactant (s) and / or the water-soluble polymer (t) [particularly those having a reverse charge to the resin particles (A) and the resin particles (B)] are used, the adsorptive power is increased and the coverage is increased. Goes up.
[3]: When the aqueous dispersion (X1) is produced, the resin (a) is a resin having an acidic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group (generally, the molecular weight per acidic functional group is If the pH of the aqueous medium is lower, the adsorptive power becomes stronger. Conversely, the higher the pH, the weaker the adsorption power.
[4]: When the aqueous dispersion (X1) is produced, the resin (a) has a basic functional group such as a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium base ( In general, the molecular weight per basic functional group is preferably 1,000 or less), the higher the pH of the aqueous medium, the stronger the adsorptive power. Conversely, the lower the pH, the weaker the adsorption power.
[5]: When the difference between the sp values of the resin (a) and the resin (b) (Δsp value) is reduced, the adsorption force increases.

In the present invention, the shape of the resin particles (D) can be controlled by the following method.
The particle shape and particle surface properties can be controlled by the difference in sp value between the resin (a) and the resin (b), the molecular weight of the resin (a), and the addition amount of the flocculant (E). When the difference in sp value is small, irregularly-shaped and smooth surface particles are easily obtained, and when the difference in sp value is large, spherical particles having a rough surface are easily obtained. Moreover, when the molecular weight of (A) is large, particles having a rough surface are easily obtained, and when the molecular weight is small, particles having a smooth surface are easily obtained. Furthermore, when the amount of the flocculant (E) added is large, the shape becomes more distorted, and when the content of the flocculant (E) is small, the shape becomes more spherical. However, if the difference in sp value between (a) and (b) is too small or too large, granulation becomes difficult. If the molecular weight of the resin (a) is too small, granulation becomes difficult. From this, the sp value difference between (a) and (b) is preferably 0.01 to 5.0, more preferably 0.1 to 3.0, and still more preferably 0.2 to 2.0. Moreover, Mw of resin (a) becomes like this. Preferably it is 100-1 million, More preferably, it is 1000-500,000, More preferably, it is 2000-200,000, Most preferably, it is 3000-100,000.

  The resin particles (C) are substantially composed of relatively small resin particles (A) and relatively large resin particles (B), and (A) is present in a form attached to the surface of (B). Or, after (A) adheres to (B), it is dissolved and / or melted, and the coating (P) from (A) is formed on the surface of (B).

In the production method of the present invention, the resin particles (C) in the aqueous dispersion (X1) are composed of resin particles (A) and resin particles (B), and (A) is attached to the surface of (B). The resin (a) having physical properties such as (Ts), (Tg), (T1 / 2), etc. within the above preferred ranges can be used, for example, in particular (b) or (b0). ) Organic solvent solution (especially the following preferred organic solvents) is preferably used in the aqueous dispersion (X1) in an amount of 10 to 50% (especially 20 to 40%), preferably 40 ° C. or less, preferably 1 By removing the solvent until it becomes less than or equal to% (particularly less than or equal to 0.5%), the resin particles (A) are dissolved in an organic solvent to form a film. An aqueous dispersion (X1) of resin particles (C) formed with There are many cases.
As said organic solvent, a thing with high affinity with (b) is preferable, and the thing similar to the said organic solvent (u) is mentioned as a specific example. Preferred among (u) are tetrahydrofuran, toluene, acetone, methyl ethyl ketone, and ethyl acetate, and more preferably ethyl acetate from the viewpoint of film formation.

  In the present invention, from the viewpoints of the particle size uniformity of the resin particles (C) and (D), the storage stability of the resin particles (D), etc., the resin particles (C) as an intermediate are 0.01 to 60%. The resin particles (A) or the resin (a) coating (P) and 40 to 99.99% (B) are preferred, and more preferably 0.1 to 50% (A) or (P). And 50 to 99.9% (B), particularly preferably 1 to 45% (A) or (P) and 55 to 99% (B).

Further, from the viewpoint of the particle size uniformity of the resin particles (C) and (D), the powder fluidity of the resin particles (D), the storage stability, etc., the resin particles (C) 5% or more, preferably 30% or more, more preferably 50% or more, particularly preferably 80% or more of the surface is covered with a coating (P) made of resin particles (A) or resin (a). . The surface coverage of (C) is obtained with a scanning electron microscope (SEM) of resin particles obtained by removing the aqueous medium in the same manner as the method of removing the aqueous medium from the aqueous dispersion of (D) described later. It can be obtained from the image analysis of the obtained image based on the following equation.
Surface coverage (%) = [area of the portion covered with the resin particles (A) or coating (P) / area of the portion covered with the resin particles (A) or coating (P) + resin particles (B ) Exposed area] × 100

From the viewpoints of particle size uniformity, powder flowability, etc. of the resin particles (D), the amount of the coating (P) of the resin particles (A) or the resin (a) is preferably relative to the weight of (D). It is 5% or less, more preferably 4% or less, particularly preferably 3% or less, and most preferably 0.1 to 1%. The amount of (A) or (P) can be determined from the heat of fusion measured by DSC based on the following equation.
Resin particle (A) or coating (P) amount (%) = [(A) or (P) heat of fusion / (A) or (P) heat of fusion + resin particle (B) heat of fusion] × 100

Further, from the viewpoints of particle size uniformity, powder flowability, etc. of the resin particles (D), the resin particles (B) formed of the resin particles (A) or the coating (P) of the resin (a) in the resin particles (D). The surface coverage is preferably 4.9% or less, more preferably 4% or less, particularly preferably 3% or less, and most preferably 0.1 to 1%. The surface coverage can be determined based on the above equation from image analysis of an image obtained with a scanning electron microscope (SEM).
As a method of adjusting the surface coverage of (A) or (P) within the above range, if resin particles higher than the desired coverage are obtained, resin particles (A) or resin (a) described later are obtained. The operation of separating and / or dissolving and removing the coating (P) may be repeated.

  In the resin particles (D), the surface of the resin particles (B) made of the second resin (b) is covered with the resin particles (A) made of the first resin (a). Or a part of the resin particles (A) may be formed into a film, and (A) and (P) may coexist. It is preferable from the point of smoothness of the resin particle surface that the surface of (B) is coated (P).

From the viewpoint of particle size uniformity, the volume distribution variation coefficient of the resin particles (C) and the resin particles (D) is preferably 30% or less, and more preferably 0.1 to 15%.
Moreover, from the particle size uniformity, the value of [volume average particle size / number average particle size] of the resin particles (C) and (D) is preferably 1.0 to 1.4, preferably 1.0 to 1.4. More preferably, it is 1.2.
The volume average particle diameter of the resin particles (C) and (D) varies depending on the application, but is generally preferably 0.1 to 300 μm. The upper limit is more preferably 250 μm, particularly preferably 200 μm, and the lower limit is more preferably 0.5 μm, particularly preferably 1 μm.
The volume average particle diameter and the number average particle diameter can be measured simultaneously with Multisizer III (manufactured by Coulter).

The resin particles (D) are the particle diameters of the resin particles (A) and the resin particles (B), and the coverage of the surface of the resin particles (B) by the coating (P) made of the resin particles (A) or the resin (a). By changing the above, desired irregularities can be imparted to the particle surface. When it is desired to improve the powder fluidity, the BET specific surface area of (D) is preferably 0.5 to 5.0 m ² / g. More preferably, it is 0.5-4.5 m < ² > / g, More preferably, it is 0.5-4.0 m < ² > / g. The BET specific surface area of the present invention is measured using a specific surface area meter such as QUANTASORB (manufactured by Yuasa Ionics) (measuring gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen). .
Similarly, from the viewpoint of powder fluidity, the surface average centerline roughness Ra of (D) is preferably 0.01 to 1.0 μm. More preferably, it is 0.01-0.9 micrometer, More preferably, it is 0.02-0.8 micrometer. Ra is a value obtained by arithmetically averaging the absolute value of the deviation between the roughness curve and its center line, and can be measured by, for example, a scanning probe microscope system (manufactured by Toyo Technica).

  The shape of the resin particles (D) is preferably spherical from the viewpoint of powder fluidity, melt leveling properties and the like. In that case, the resin particles (D) are only the resin particles (B), or the film (P) made of the resin (a) is attached to the resin particles (B), and (B) is spherical. In the case where the resin particles (A) are attached to (B), it is preferable that (A) and (B) are also spherical. (D) preferably has an average circularity of 0.95 to 1.00. The average circularity is more preferably 0.96 to 1.0, and particularly preferably 0.97 to 1.0. The average circularity is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. Specifically, it is measured using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 ml of water from which impure solids have been removed in advance is added, and 0.1 to 0.5 ml of a surfactant (Dry Well; manufactured by Fuji Photo Film Co., Ltd.) is added as a dispersant. Add about 1-9.5g. The suspension in which the sample is dispersed is subjected to a dispersion treatment with an ultrasonic disperser (Ultrasonic Cleaner Model VS-150; manufactured by Wellboclear) for about 1 to 3 minutes to obtain a dispersion concentration of 3,000 to 10,000 / μL. Then, the shape and distribution of the resin particles are measured.

The resin particles (D) obtained by the production method of the present invention preferably have a coating (P) attached to the resin particles (B), but if they are resin particles (A), the resin particles The particle size ratio of (A) to the resin particles (B), the coverage of the surface of the resin particles (B) with the resin particles (A) in the aqueous dispersion (X1), and the resin particles in the aqueous dispersion (X1) (B) By changing the depth at which the resin particle (A) is embedded on the resin particle (B) side on the aqueous medium interface, the particle surface is smoothed, or desired irregularities are imparted to the particle surface. can do.
The coverage of the surface of the resin particle (B) with the resin particle (A) and the depth at which the resin particle (A) is embedded on the resin particle (B) side can be controlled by the following method.
[1]: When the aqueous dispersion (X1) composed of the resin particles (C) is produced, if the resin particles (A) and the resin particles (B) have positive and negative charges, the coverage and depth are reduced. growing. In this case, the coverage and the depth increase as the electric charges of the resin particles (A) and the resin particles (B) are increased.
[2]: When producing the aqueous dispersion (X1) composed of the resin particles (C), the resin particles (A) and the resin particles (B) have the same polarity (both positive or both negative). If it has, it will tend to decrease the coverage and reduce the depth. In this case, generally, when the activator (s) and / or the water-soluble polymer (t) [particularly those having a reverse charge to the resin particles (A) and the resin particles (B)] are used, the coverage is increased. Moreover, when using water-soluble polymer (t), depth becomes small, so that the molecular weight of water-soluble polymer (t) is large.
[3]: When the aqueous dispersion (X1) comprising the resin particles (C) is produced, the resin (a) has an acidic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group (generally an acidic functional group). The molecular weight per group is preferably 1,000 or less), the lower the pH of the aqueous medium, the greater the coverage and depth. Conversely, the higher the pH, the smaller the coverage and depth.
[4]: When the aqueous dispersion (X1) comprising the resin particles (C) is produced, the resin (a) is a base such as a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium base. When the resin has a functional functional group (generally, the molecular weight per basic functional group is preferably 1,000 or less), the higher the pH of the aqueous medium, the greater the coverage and depth. Conversely, the lower the pH, the smaller the coverage and depth.
[5]: The coverage and depth increase as the difference in sp value between resin (a) and resin (b) decreases.

  In the production method of the present invention, the aqueous dispersion (X2) of the resin particles (D) is formed from the resin particles (C) and the resin particles (A) or the coating (P) of the resin (a) and the resin. After removing the particles (B), the resin particles (A) or the coating (P) are separated and removed from the aqueous dispersion, or the resin particles (B) are not dissolved in the aqueous dispersion. It can be obtained by dissolving the resin particles (A) or the coating (P). The dissolved matter of the resin particles (A) or the coating (P) may be separated and removed as necessary. Furthermore, resin particles (D) are obtained by removing the aqueous medium from the aqueous dispersion (X2) of resin particles (D).

In the aqueous dispersion (X1) of the resin particles (C), as a method of desorbing the resin particles (A) or the coating (P) of the resin (a) and the resin particles (B),
[1] Method for ultrasonic treatment of aqueous dispersion of resin particles (C) [2] Dilute the aqueous dispersion of resin particles (C) with a large amount of water or a water-soluble organic solvent such as methanol, ethanol or acetone. , A method of applying shear by stirring [3] a method of adding an acid, alkali or inorganic salt to the aqueous dispersion of resin particles (C) and applying shear by stirring [4] an aqueous dispersion of resin particles (C) Method of heating and applying shear by stirring [5] When the aqueous dispersion of resin particles (C) contains an organic solvent [the organic solvent solution of resin (a) and / or the resin (b) organic solvent solution is in an aqueous medium In the case where the organic solvent is dissolved in the aqueous medium, a method for removing the solvent is exemplified.

In the aqueous dispersion (X1) of the resin particles (C), as a method for dissolving the resin particles (A) or the coating (P),
[1] When the resin (a) is a resin having an acidic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group (generally, the molecular weight per acidic functional group is preferably 1,000 or less) A method of adding an alkali such as sodium hydroxide, potassium hydroxide, ammonia, DBU or an aqueous solution thereof to the aqueous dispersion [2] Resin (a) is a primary amino group, secondary amino group, tertiary amino group In the case of a resin having a basic functional group such as a quaternary ammonium base (generally preferably the molecular weight per basic functional group is 1,000 or less), hydrochloric acid, sulfuric acid, Method of adding acids such as phosphoric acid and acetic acid or an aqueous solution thereof [3] When resin (a) is dissolved in a specific organic solvent (u) {generally, the SP value of resin (a) and organic solvent (u) The difference is less than 2.5 Preferred} that that method such as adding a specific organic solvent (u) in the aqueous dispersion is exemplified.
As a method of removing the resin particles (A) or the coating (P), a method of dissolving the resin particles is preferable, and a method of adding an alkali or an aqueous solution thereof to a resin having an acidic functional group and a basic functional group are more preferable. In particular, it is a method of adding an acid or an aqueous solution thereof to a resin having an acid, and a method of adding an alkali or an aqueous solution thereof to a resin having an acidic functional group is particularly preferable.

As a method for separating and removing the resin particles (A) or the coating (P) or a dissolved product thereof from the aqueous dispersion,
[1] A method of filtering using a filter paper, a filter cloth, a mesh, etc. having a certain opening, and filtering out only the resin particles (B). Examples thereof include a method of removing the resin particles (A) or the coating (P) contained therein or a dissolved product thereof.

As a method of removing the aqueous medium from the aqueous dispersion (X2) to obtain the resin particles (D),
[1] A method of drying an aqueous dispersion under reduced pressure or normal pressure [2] A method of solid-liquid separation with a centrifuge, a spacula filter, a filter press, etc., and drying the resulting powder [3] An aqueous dispersion Method of freezing and drying (so-called freeze drying)
Etc. are exemplified.
In the above [1] and [2], when the obtained powder is dried, it can be performed using a known facility such as a fluidized bed dryer, a vacuum dryer, or a circulating dryer.
Moreover, it can classify using an air classifier etc. as needed, and can also be made into a predetermined particle size distribution.

Additives (pigments, fillers, antistatic agents, colorants, release agents, charge control) in the resin particles (A) or coatings (P) and / or resin particles (B) constituting the resin particles (D) Agents, ultraviolet absorbers, antioxidants, anti-blocking agents, heat stabilizers, flame retardants, etc.) may be mixed. As a method of adding an additive to (A) or the coating (P) or (B), the aqueous dispersion (X1) may be mixed in an aqueous medium, but the resin (a) may be mixed in advance. Alternatively, it is more preferable that the resin (b) or precursor (b0) and the additive are mixed and then the mixture is added and dispersed in the aqueous dispersion (W).
In the present invention, the additive does not necessarily need to be mixed when the particles are formed in the aqueous dispersion (W), and may be added after the particles are formed. For example, after forming particles containing no colorant, a colorant may be added by a known dyeing method, or the additive may be impregnated with the organic solvent (u) and / or the plasticizer (v). it can.

Moreover, as an additive, it is preferable that the resin particles (B) contain the wax (c) together with the resin (b) because the releasability is improved. In some cases, a modified wax (d) grafted with a vinyl polymer chain may be contained, which is preferable because the heat-resistant storage stability is further improved.
The content of (c) in (B) is preferably 20% or less, more preferably 1 to 15%. The content of (d) is preferably 10% or less, more preferably 8% or less. The total content of (c) and (d) is preferably 25% or less, more preferably 1 to 20%.

The wax (c) is dispersed in the resin (b) after being melt-kneaded and / or heated and dissolved and mixed in the presence of the organic solvent (u). Alternatively, it is dispersed in the resin (b) after being previously melt-kneaded in the absence of the modified wax (d) and / or an organic solvent and / or heated, dissolved and mixed in the presence of the organic solvent (u).
Examples of the wax (c) include synthetic wax and natural wax. Examples of the synthetic wax include polyolefin wax, examples of the natural wax include paraffin wax, microcrystalline wax, carnauba wax, carbonyl group-containing wax, and mixtures thereof. Of these, paraffin wax (c1) and carnauba wax (c2) are particularly preferable. Examples of (c1) include petroleum wax mainly composed of a linear saturated hydrocarbon having a melting point of 50 to 90 ° C. and a carbon number of 20 to 36, and (c2) includes a melting point of 50 to 90 ° C. and a carbon number of 16 -36 animal and plant waxes.
Further, from the viewpoint of releasability, Mn in (c) is preferably 400 to 5000, more preferably 1000 to 3000, and particularly 1500 to 2000. In the above and below, the Mn of the wax is measured using GPC (solvent: orthodichlorobenzene, reference material: polystyrene).

  The wax (c) is dispersed in the resin (b) after being melt-kneaded in the absence of solvent and / or heat-dissolved and mixed in the presence of the organic solvent (u) with the modified wax (d) grafted with the vinyl polymer chain. Preferably it is done. By the coexistence of the modified wax (d) during the wax dispersion treatment by this method, the wax base portion of (d) is efficiently adsorbed on the surface or partly entangled in the wax matrix structure, The affinity between the surface of the wax (c) and the resin (b) is improved, and (c) can be more uniformly encapsulated in the resin particles (B), and the dispersion state can be easily controlled.

  The modified wax (d) is obtained by grafting a vinyl polymer chain onto the wax. Examples of the wax used in (d) include the same waxes as the wax (c), and preferred ones are also the same. Examples of the vinyl monomer constituting the vinyl polymer chain of (d) include those similar to the monomers (1) to (10) constituting the vinyl resin. Among these, (1), ( 2) and (6). The vinyl polymer chain may be a homopolymer of a vinyl monomer or a copolymer.

The amount of the wax component (including the unreacted wax) in the modified wax (d) is preferably 0.5 to 99.5%, more preferably 1 to 80%, particularly preferably 5 to 50%, and most preferably 10. ~ 30%. The Tg of (d) is preferably 40 to 90 ° C, more preferably 50 to 80 ° C, from the viewpoint of heat resistant storage stability of the resin particles (D).
Mn of (d) is preferably 1500 to 10,000, particularly 1800 to 9000. When Mn is in the range of 1500 to 10,000, the mechanical strength of the resin particles (D) is good.

The modified wax (d) is prepared by, for example, dissolving or dispersing the wax (c) in an organic solvent (for example, toluene or xylene) and heating to 100 to 200 ° C., and then converting the vinyl monomer into a peroxide initiator (benzoyl peroxide, diter It is obtained by dropping the organic solvent and distilling the organic solvent after the polymerization.
The amount of the peroxide-based initiator in the synthesis of the modified wax (d) is preferably 0.2 to 10%, more preferably 0.5 to 5%, based on the total weight of the raw material (d).

As the peroxide polymerization initiator, an oil-soluble peroxide polymerization initiator and a water-soluble peroxide polymerization initiator are used.
Specific examples of these initiators include those described above.

As a method of mixing the wax (c) and the modified wax (d), [1] a method of melt kneading at a temperature equal to or higher than the melting point of each, [2] (c) and (d) in the organic solvent (u) A method of dissolving or suspending, then precipitating in a liquid by cooling crystallization, solvent crystallization or the like, or precipitating in a gas by spray drying or the like, [3] (c) and (d) as an organic solvent Examples of the method include a method of dissolving or suspending the powder in the inside and then performing mechanical wet pulverization with a disperser. Among these, the method [2] is preferable.
As a method of dispersing the wax (c) and the modified wax (d) in (b), (c), (d), and (b) are made into an organic solvent solution or a dispersion, respectively, And the like.

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

Production Example 1
[Synthesis of titanium-containing catalyst]
Place 1000 parts of ethyl acetate and 800 parts of terephthalic acid in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube capable of bubbling in the liquid, and gradually raise the temperature to 60 ° C. while bubbling in the liquid with nitrogen. Then, while adding 600 parts of titanium tetraisopropoxide dropwise, the mixture was reacted at 60 ° C. for 4 hours to obtain a slurry-like reaction mixture. The reaction mixture is filtered off with a filter paper and dried at 40 ° C./20 kPa · s, so that a titanium-containing catalyst (t1) composed of a mixture of titanium triisopropoxyterephthalate and unreacted terephthalic acid (titanium triisopropoxyterephthalate concentration 65%). )

Production Example 2
[Synthesis of titanium-containing catalyst]
Titanium diisopropoxybis (triethanolaminate) 1617 parts and ion-exchanged water 126 parts are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introducing pipe capable of bubbling in liquid, and bubbling in liquid with nitrogen. Then, the temperature was gradually raised to 90 ° C. and reacted (hydrolyzed) at 90 ° C. for 4 hours to obtain titanium dihydroxybis (triethanolaminate). Furthermore, the titanium-containing catalyst (t2) which consists of an intramolecular polycondensate represented by a following formula was obtained by making it react (dehydration condensation) under reduced pressure for 2 hours at 100 degreeC.

Production Example 3 (Production of aqueous dispersion of resin particles (A))
In a reaction vessel equipped with a stirrer and a thermometer, 130 parts of isopropanol was charged and, under stirring, 10 parts of butyl acrylate, 67 parts of vinyl acetate, 15 parts of maleic anhydride, sodium methacryloyloxypolyoxyalkylenesulfate (eleminol) A mixed solution of 6 parts RS-30 (manufactured by Sanyo Chemical Industries) and 2 parts of benzoyl peroxide (25% water-containing product) was added dropwise over 120 minutes. 50 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W1]. The volume average particle diameters of [fine particle dispersion W1] measured by LA-920 and ELS-800 were both 0.10 μm. A portion of [fine particle dispersion W1] was dried to isolate the resin component. The resin component had a Tg of 71 ° C. by DSC measurement, a softening start temperature of 105 ° C., and an outflow temperature of 169 ° C.

Production Example 4 (Production of aqueous dispersion of resin particles (A))
In a reaction vessel equipped with a stirrer and a thermometer, 130 parts of isopropanol was charged. The mixed solution was added dropwise over 120 minutes. 50 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W2]. The volume average particle diameters of [fine particle dispersion W2] measured by LA-920 and ELS-800 were both 0.09 μm. A portion of [fine particle dispersion W2] was dried to isolate the resin component. Tg by DSC measurement of the resin was 72 ° C., the softening start temperature was 100 ° C., and the outflow temperature was 164 ° C.

Production Example 5 (Production of aqueous dispersion of resin particles (A))
A reaction vessel equipped with a stir bar and thermometer was charged with 130 parts of isopropanol, and under stirring, 71 parts of methyl methacrylate, 143 parts of vinyl acetate, 73 parts of acrylic acid, and 25 parts of benzoyl peroxide (25% water-containing product) were mixed. The solution was added dropwise over 120 minutes. 50 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W3]. The volume average particle diameters of [fine particle dispersion W3] measured by LA-920 and ELS-800 were both 0.05 μm. A portion of [fine particle dispersion W3] was dried to isolate the resin component. Tg by DSC measurement of the resin was 50 ° C., the softening start temperature was 60 ° C., and the outflow temperature was 120 ° C.

Production Example 6 (Production of aqueous dispersion of resin particles (A))
In a reaction vessel equipped with a stir bar and a thermometer, 130 parts of isopropanol was charged. Under stirring, 29 parts of 2-decyltetradecyl methacrylate, 214 parts of vinyl acetate, 43 parts of methacrylic acid, benzoyl peroxide (25% water-containing product) 25 Part of the mixed solution was added dropwise over 120 minutes. 50 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W4]. The volume average particle diameters of [fine particle dispersion W4] measured by LA-920 and ELS-800 were both 0.09 μm. A part of [fine particle dispersion W4] was dried to isolate the resin component. Tg by DSC measurement of the resin content was 75 ° C., the softening start temperature was 103 ° C., and the outflow temperature was 167 ° C.

Production Example 7 (Production of aqueous dispersion of resin particles (A))
In a reaction vessel equipped with a stirrer and a thermometer, 130 parts of isopropanol was charged. A mixed solution of 8 parts by Kasei Kogyo) and 25 parts of benzoyl peroxide (25% water-containing product) was added dropwise over 120 minutes. 29 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W5]. The volume average particle diameters of [fine particle dispersion W5] measured by LA-920 and ELS-800 were both 0.05 μm. A portion of [fine particle dispersion W5] was dried to isolate the resin component. Tg by DSC measurement of the resin content was 120 ° C., the softening start temperature was 160 ° C., and the outflow temperature was 250 ° C.

Production Example 8 (Production of aqueous dispersion of resin particles A)
In a reaction vessel equipped with a stir bar and a thermometer, 177 parts of polyester (Mn1000) obtained from adipic acid and 1,4-butanediol (molar ratio 1: 1), 1,2-propylene glycol (hereinafter referred to as propylene glycol) Description) 7 parts, 72 parts of dimethylolpropionic acid, 4 parts of 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, and 500 parts of acetone were charged. To this solution, 246 parts of isophorone diisocyanate (IPDI) was charged and reacted at 55 ° C. for 11 hours to obtain [Urethane Prepolymer 1]. Triethylamine was added to the prepolymer to neutralize 100 equivalent% of the carboxylic acid derived from dimethylolpropionic acid with amine. This solution was added to 1500 parts of water with stirring and emulsified. Further, 320 parts of water, 9 parts of ethylenediamine and 6 parts of n-butylamine were added, and an elongation reaction was carried out at 50 ° C. for 4 hours to obtain an aqueous dispersion of urethane resin [fine particle dispersion W6]. The volume average particle diameter of [fine particle dispersion W6] measured by ELS-800 was 0.09 μm. A part of [Fine Particle Dispersion W6] was dried to isolate the resin component. The Tg was 80 ° C., the softening start temperature was 105 ° C., and the outflow temperature was 160 ° C. by flow tester measurement.

Production Example 9 (Production of aqueous dispersion of resin particles A)
In a reaction vessel equipped with a stir bar and a thermometer, 753 parts of water, 8 parts of sodium salt of alkylallylsulfosuccinic acid (Eleminol JS-2, Sanyo Chemical Industries), 58 parts of styrene, 58 parts of methacrylic acid, 77 butyl acrylate Parts, 1 part of ammonium persulfate, and 9 parts of a surfactant (polyoxysorbitan monooleate) were stirred at 300 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours. Liquid W7] was obtained. The volume average particle diameters of [fine particle dispersion W7] measured by LA-920 and ELS-800 were both 0.07 μm. A portion of [fine particle dispersion W7] was dried to isolate the resin component. The resin component had a Tg of 60 ° C. by DSC measurement, a softening start temperature of 110 ° C., and an outflow temperature of 198 ° C.

Production Example 10 (Production of aqueous dispersion of resin particles (A))
In a reaction vessel equipped with a stirrer and a thermometer, 115 parts of isopropanol was charged. Under stirring, 30 parts of butyl acrylate, 30 parts of styrene, 40 parts of methacrylic acid, sodium salt of alkylallylsulfosuccinic acid (Eleminol JS-2, Sanyo) A mixed solution of 8 parts by Kasei Kogyo) and 10 parts of benzoyl peroxide (25% water-containing product) was added dropwise over 120 minutes. 29 parts of this polymerization solution was further added dropwise to 60 parts of ion-exchanged water with stirring to obtain an aqueous dispersion [fine particle dispersion W8]. The volume average particle diameters of [fine particle dispersion W8] measured by LA-920 and ELS-800 were both 0.05 μm. Part of [fine particle dispersion W8] was dried to isolate the resin component. Tg by DSC measurement of the resin was 50 ° C., the softening start temperature was 140 ° C., and the outflow temperature was 210 ° C.

Production Example 11 (Production of resin (b))
[Synthesis of linear polyester]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 701 parts (18.8 moles) of propylene glycol, 716 parts (7.5 moles) of dimethyl terephthalate, 180 parts of adipic acid (2.5 moles) And 0.8 part of a titanium-containing catalyst (t1) as a condensation catalyst were allowed to react for 8 hours while distilling off the methanol produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature up to 230 ° C., the reaction is performed for 4 hours while distilling off the propylene glycol and water generated under a nitrogen stream, and further the reaction is performed under reduced pressure of 5 to 20 mmHg, and the softening point becomes 150 ° C. It was taken out at the time. The recovered propylene glycol was 316 parts (8.5 mol). The taken-out resin was cooled to room temperature and then pulverized into particles to obtain [Polyester b1]. Mn of [Polyester b1] was 8000.
The number of moles in () means a relative molar ratio (the same applies hereinafter).

Production Example 12 (Production of resin (b))
[Synthesis of nonlinear polyester]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 557 parts (17.5 moles) of propylene glycol, 569 parts (7.0 moles) of dimethyl terephthalate, 184 parts (3.0 moles) of adipic acid ), And 0.7 part of a titanium-containing catalyst (t1) as a condensation catalyst, and reacted for 8 hours at 180 ° C. while distilling off the produced methanol under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 175 parts (5.5 mol). Next, the mixture was cooled to 180 ° C., 121 parts (1.5 mol) of trimellitic anhydride was added, reacted for 2 hours under normal pressure sealing, reacted at 220 ° C. and normal pressure, and when the softening point reached 180 ° C. After taking out and cooling to room temperature, it was pulverized and granulated to obtain [Polyester b2]. Mn of [Polyester b2] was 8500.

Production Example 13 (Production of resin (b))
[Synthesis of linear polyester]
430 parts of bisphenol A / PO2 molar adduct, 300 parts of bisphenol A / PO3 molar adduct, 257 parts of terephthalic acid, 65 parts of isophthalic acid, maleic anhydride 10 parts and 5.3 parts of a titanium-containing catalyst (t2) as a polycondensation catalyst were added and reacted at 220 ° C. for 10 hours while distilling off the water generated in a nitrogen stream. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg, and when the acid value reached 4, it was taken out, cooled to room temperature and pulverized to obtain [Polyester b3]. Mn of [Polyester b3] was 6980.

Production Example 14 (Production of resin (b))
[Synthesis of nonlinear polyester]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 350 parts of bisphenol A / EO 2 mol adduct, 326 parts of bisphenol A / PO 3 mol adduct, 278 parts of terephthalic acid, 40 parts of phthalic anhydride and polycondensation As a catalyst, 5.0 parts of a titanium-containing catalyst (t2) was added and reacted at 230 ° C. for 10 hours while distilling off water generated under a nitrogen stream. Next, the reaction is carried out under reduced pressure of 5 to 20 mmHg. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., added with 62 parts of trimellitic anhydride, taken out after reaction for 2 hours under sealed at normal pressure, and cooled to room temperature. To obtain [Polyester b4]. Mn of [Polyester b4] was 11400.

Production Example 15
In a reaction vessel equipped with a stir bar and a thermometer, 2000 parts of polycaprolactone diol having a hydroxyl number of 56 (Placcel L220AL, manufactured by Daicel Chemical Industries, Ltd.) is charged, heated to 110 ° C., and dehydrated under a reduced pressure of 3 mmHg for 1 hour. Went. Subsequently, 457 parts of IPDI were added and reacted at 110 ° C. for 10 hours to obtain [Urethane Prepolymer 1] having an isocyanate group at the terminal. The NCO content of [Urethane Prepolymer 1] was 3.6%.

Production Example 16
In a reaction vessel equipped with a stirrer and a thermometer, 50 parts of ethylenediamine and 300 parts of MIBK were charged and reacted at 50 ° C. for 5 hours to obtain [curing agent 1] which is a ketimine compound.

Production Example 17 (Production of Colorant Dispersion)
In a beaker, 20 parts of copper phthalocyanine, 4 parts of a colorant dispersant (Solspers 28000; manufactured by Avicia Co., Ltd.), 20 parts of [Polyester b2] and 56 parts of ethyl acetate were stirred and dispersed uniformly. Phthalocyanine was finely dispersed to obtain [Colorant Dispersion Liquid 1]. The volume average particle diameter of [Colorant Dispersion Liquid 1] measured by LA-920 was 0.3 μm.

Production Example 18 (Production of colorant dispersion)
In a beaker, 40 parts of copper phthalocyanine, 4 parts of a colorant dispersant (Solspers 28000; manufactured by Avicia Co., Ltd.), and 56 parts of ethyl acetate were stirred and uniformly dispersed. [Colorant dispersion 2] was obtained. The volume average particle diameter of [Colorant Dispersion Liquid 2] measured by LA-920 was 0.2 μm.

Production Example 19 (Production of modified wax)
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 454 parts of xylene and 150 parts of low molecular weight polyethylene (Sanwa Kasei Kogyo Co., Ltd. Sun Wax LEL-400: softening point 128 ° C.) were added, and after nitrogen replacement, 170 parts were obtained. The temperature was raised to 0 ° C. and dissolved sufficiently, and a mixed solution of 595 parts of styrene, 255 parts of methyl methacrylate, 34 parts of di-t-butylperoxyhexahydroterephthalate and 119 parts of xylene was added dropwise at 170 ° C. over 3 hours for polymerization. And kept at this temperature for 30 minutes. Next, the solvent was removed to obtain [modified wax 1]. The sp value of the graft chain of [modified wax 1] was 10.35 (cal / cm ³ ) ^1/2 , Mn was 1872, Mw was 5194, and Tg was 56.9 ° C.

Production Example 20 (Production of wax dispersion)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of paraffin wax (melting point: 73 ° C.), 1 part of [modified wax 1] and 33 parts of ethyl acetate are added, heated to 78 ° C. and sufficiently dissolved. After cooling to 30 ° C. over time, the wax was crystallized into fine particles and further wet-pulverized with Ultraviscomyl (manufactured by IMEX) to obtain [Wax Dispersion 1].

Production Example 21 (Production of wax dispersion)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of carnauba wax (melting point 70 ° C.) and 33 parts of ethyl acetate are added, heated to 78 ° C. to dissolve sufficiently, and cooled to 30 ° C. in 1 hour. The wax was crystallized into fine particles and wet-pulverized with Ultraviscomyl (manufactured by Imex) to obtain [Wax Dispersion 2].

Production Example 22 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b1] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin Solution 1].

Production Example 23 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b2] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin Solution 2].

Production Example 24 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b3] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin Solution 3].

Production Example 25 (Production of resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Polyester b4] and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain [Resin Solution 4].

Example 1
Place 48 parts of [resin solution 1], 12 parts of [resin solution 2], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1] in a beaker at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 97 parts of ion-exchanged water, 15.4 parts of [fine particle dispersion W1], 1 part of sodium carboxymethylcellulose, and 5 parts of magnesium sulfate were uniformly dissolved. Next, at 25 ° C., 75 parts of [resin solution 1A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less, and adhered to the surface [fine particle dispersion W1]. An aqueous dispersion (X-1) of resin particles in which the resin particles derived therefrom were coated was obtained. Next, 100 parts of a 5% aqueous sodium hydroxide solution is added to 100 parts of (X-1), and the temperature is adjusted to 40 ° C. using a TK homomixer (manufactured by Tokushu Kika) and mixed for 10 minutes at 12,000 rpm. Then, after the coating derived from [fine particle dispersion W1] adhering to the surface was dissolved, it was separated by filtration, dried at 40 ° C. for 18 hours, the volatile content was reduced to 0.5% or less, and the resin particles (D− 1) was obtained.

Example 2
Place 48 parts of [resin solution 1], 12 parts of [resin solution 2], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1] in a beaker at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 102 parts of ion exchange water, 10.5 parts of [fine particle dispersion W1], 1 part of sodium carboxymethylcellulose, and 5 parts of sodium chloride were uniformly dissolved. Next, at 25 ° C., 75 parts of [resin solution 1A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less, and adhered to the surface [fine particle dispersion W1]. An aqueous dispersion (X-2) of resin particles in which the resin particles derived therefrom were coated was obtained. Next, 100 parts of a 5% aqueous sodium hydroxide solution is added to 100 parts of (X-2), and the temperature is adjusted to 40 ° C. using a TK homomixer (manufactured by Tokushu Kika) and mixed for 10 minutes at 12,000 rpm. Then, after the coating derived from [fine particle dispersion W1] adhering to the surface was dissolved, it was separated by filtration, dried at 40 ° C. for 18 hours, the volatile content was reduced to 0.5% or less, and the resin particles (D− 2) was obtained.

Example 3
Place 48 parts of [resin solution 1], 12 parts of [resin solution 2], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1] in a beaker at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 102 parts of ion exchange water, 10.5 parts of [fine particle dispersion W2], 1 part of sodium carboxymethylcellulose, and 5 parts of sodium chloride were uniformly dissolved. Next, at 25 ° C., 75 parts of [resin solution 1A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration became 0.5% or less, and adhered to the surface [fine particle dispersion W2]. An aqueous dispersion (X-3) of resin particles coated with resin particles derived therefrom was obtained. Next, 100 parts of 5% sodium hydroxide aqueous solution is added to 100 parts of (X-3), and the temperature is adjusted to 40 ° C. using a TK homomixer (manufactured by Tokushu Kika), and mixed for 10 minutes at 12,000 rpm. Then, after the coating derived from [fine particle dispersion W2] adhering to the surface was dissolved, it was separated by filtration, dried at 40 ° C. for 18 hours, the volatile content was reduced to 0.5% or less, and resin particles (D− 3) was obtained.

Example 4
In a beaker, put 48 parts of [resin solution 1], 6 parts of [prepolymer 1], 0.2 part of [curing agent 1], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1]. The mixture was stirred at 8,000 rpm with a TK homomixer at 25 ° C., and uniformly dissolved and dispersed to obtain [resin solution 1B].
In a beaker, 102 parts of ion exchange water, 11 parts of [fine particle dispersion W1], 1 part of sodium carboxymethylcellulose, and 5 parts of sodium chloride were uniformly dissolved. Then, at 25 ° C., 75 parts of [resin solution 1B] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised, and ethyl acetate was distilled off at 35 ° C. until the concentration became 0.5% or less. An aqueous dispersion (X-4) of resin particles in which the resin particles derived therefrom were coated was obtained. Next, 100 parts of a 5% sodium hydroxide aqueous solution is added to 100 parts of (X-4), and the temperature is adjusted to 40 ° C. using a TK homomixer (manufactured by Tokushu Kika), and mixed for 10 minutes at 12,000 rpm. Then, after the coating derived from [fine particle dispersion W1] adhering to the surface was dissolved, it was separated by filtration, dried at 40 ° C. for 18 hours, the volatile content was reduced to 0.5% or less, and the resin particles (D− 4) was obtained.

Example 5
Place 48 parts of [resin solution 1], 12 parts of [resin solution 2], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1] in a beaker at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of [fine particle dispersion W1], 1 part of sodium carboxymethylcellulose, and 10 parts of sodium chloride were uniformly dissolved. Next, at 25 ° C., 75 parts of [resin solution 1A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Then, this mixed liquid was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less, and adhered to the surface [fine particle dispersion W1]. An aqueous dispersion (X-5) of resin particles coated with resin particles derived therefrom was obtained. Next, 100 parts of 5% aqueous sodium hydroxide is added to 100 parts of (X-5), and the temperature is adjusted to 40 ° C. using a TK homomixer (manufactured by Tokushu Kika) and mixed for 10 minutes at 12,000 rpm. Then, after the coating derived from [fine particle dispersion W1] adhering to the surface was dissolved, it was separated by filtration, dried at 40 ° C. for 18 hours, the volatile content was reduced to 0.5% or less, and the resin particles (D− 5) was obtained.

Example 6
Place 48 parts of [resin solution 1], 12 parts of [resin solution 2], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1] in a beaker at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 102 parts of ion exchange water, 10.5 parts of [fine particle dispersion W4], 1 part of sodium carboxymethylcellulose and 5 parts of sodium chloride were uniformly dissolved. Next, at 25 ° C., 75 parts of [resin solution 1A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Next, this mixed liquid was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less, and adhered to the surface [fine particle dispersion W4]. An aqueous dispersion (X-6) of resin particles coated with resin particles derived therefrom was obtained. Next, 100 parts of 5% aqueous sodium hydroxide solution is added to 100 parts of (X-6), and the temperature is adjusted to 40 ° C. using a TK homomixer (made by Tokushu Kika), and mixed for 10 minutes at 12,000 rpm. Then, after the coating derived from [fine particle dispersion W4] adhering to the surface was dissolved, it was separated by filtration, dried at 40 ° C. for 18 hours, the volatile content was reduced to 0.5% or less, and the resin particles (D− 6) was obtained.

Example 7
Place 48 parts of [resin solution 1], 12 parts of [resin solution 2], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1] in a beaker at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 102 parts of ion-exchanged water, 10.5 parts of [fine particle dispersion W1], 1 part of sodium carboxymethylcellulose, and 5 parts of calcium chloride were uniformly dissolved. Next, at 25 ° C., 75 parts of [resin solution 1A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less, and adhered to the surface [fine particle dispersion W1]. An aqueous dispersion (X-7) of resin particles coated with resin particles derived therefrom was obtained. Next, 100 parts of 5% aqueous sodium hydroxide solution is added to 100 parts of (X-7), and the temperature is adjusted to 40 ° C. using a TK homomixer (manufactured by Tokushu Kika), and mixed for 10 minutes at 12,000 rpm. Then, after the coating derived from [fine particle dispersion W1] adhering to the surface was dissolved, it was separated by filtration, dried at 40 ° C. for 18 hours, the volatile content was reduced to 0.5% or less, and the resin particles (D− 7) was obtained.

Example 8
In a beaker, 48 parts of [resin solution 1], 12 parts of [resin solution 3], 27 parts of [wax dispersion 2] and 10 parts of [colorant dispersion 1] are placed at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm, and uniformly dissolved and dispersed to obtain [resin solution 2A].
In a beaker, 102 parts of ion exchange water, 10.5 parts of [fine particle dispersion W1], 1 part of sodium carboxymethylcellulose, and 5 parts of aluminum chloride were uniformly dissolved. Next, at 25 ° C., 75 parts of [resin solution 2A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less, and adhered to the surface [fine particle dispersion W1]. An aqueous dispersion (X-8) of resin particles coated with resin particles derived therefrom was obtained. Next, 100 parts of a 5% aqueous sodium hydroxide solution is added to 100 parts of (X-8), and the temperature is adjusted to 40 ° C. using a TK homomixer (manufactured by Tokushu Kika), and mixed for 10 minutes at 12,000 rpm. Then, after the coating derived from [fine particle dispersion W1] adhering to the surface was dissolved, it was separated by filtration, dried at 40 ° C. for 18 hours, the volatile content was reduced to 0.5% or less, and the resin particles (D− 8) was obtained.

Example 9
Place 48 parts of [resin solution 1], 12 parts of [resin solution 2], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1] in a beaker at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 90.4 parts of ion exchange water, 2.6 parts of [fine particle dispersion W3], 1 part of sodium carboxymethylcellulose, and 25 parts of magnesium sulfate were uniformly dissolved. Next, at 25 ° C., 75 parts of [resin solution 1A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stirring bar and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less, and adhered to the surface [fine particle dispersion W3]. An aqueous dispersion (X-9) of resin particles in which the resin particles derived therefrom were coated was obtained. Next, 100 parts of 5% aqueous sodium hydroxide is added to 100 parts of (X-9), and the temperature is adjusted to 40 ° C. using a TK homomixer (manufactured by Tokushu Kika), and mixed for 10 minutes at 12,000 rpm. Then, after the coating derived from [fine particle dispersion W3] adhering to the surface was dissolved, it was filtered and dried at 40 ° C. for 18 hours to reduce the volatile content to 0.5% or less to obtain resin particles (D- 9) was obtained.

Example 10
In a beaker, 48 parts of [resin solution 4], 12 parts of [resin solution 3], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 2] are placed at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm, and uniformly dissolved and dispersed to obtain [resin solution 3A].
In a beaker, 75.6 parts of ion exchange water, 41.8 parts of [fine particle dispersion W5], 1 part of sodium carboxymethylcellulose, 0.5 part of sodium chloride, and 0.1 part of magnesium sulfate were uniformly dissolved. Then, at 25 ° C., 75 parts of [resin solution 3A] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less, and adhered to the surface [fine particle dispersion W5]. An aqueous dispersion (X-10) of resin particles coated with resin particles derived therefrom was obtained. Next, 100 parts of a 5% aqueous sodium hydroxide solution is added to 100 parts of (X-10), and the temperature is adjusted to 40 ° C. using a TK homomixer (manufactured by Tokushu Kika) and mixed for 10 minutes at 12,000 rpm. Then, after the coating derived from [fine particle dispersion W5] adhering to the surface was dissolved, it was separated by filtration and dried at 40 ° C. for 18 hours to reduce the volatile content to 0.5% or less to obtain resin particles (D− 10) was obtained.

Comparative Example 1
Place 48 parts of [resin solution 1], 12 parts of [resin solution 2], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1] in a beaker at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of [fine particle dispersion W7], 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ELEMINOL MON-7”) ) 10 parts was added and dissolved uniformly. Otherwise, in the same manner as in Example 2, an aqueous dispersion (X′-11) of resin particles having resin particles derived from [fine particle dispersion W7] adhered to the surface was obtained. Next, 100 parts of a 5% aqueous sodium hydroxide solution is added to 100 parts of (X′-11), and the temperature is adjusted to 40 ° C. using a TK homomixer (manufactured by Tokushu Kika) for 10 minutes at 12,000 rpm. After mixing and dissolving the resin particles derived from the [fine particle dispersion W7] adhering to the surface, the resin particles were separated by filtration and dried at 40 ° C. for 18 hours to reduce the volatile content to 0.5% or less. D′-11) was obtained.

Comparative Example 2
Place 48 parts of [resin solution 1], 12 parts of [resin solution 2], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1] in a beaker at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 107 parts of ion-exchanged water, 10.5 parts of [fine particle dispersion W8] and 1 part of sodium carboxymethylcellulose were uniformly dissolved. Otherwise, in the same manner as in Example 2, an aqueous dispersion (X′-12) of resin particles in which resin particles derived from [fine particle dispersion W8] attached to the surface were coated was obtained. Next, 100 parts of a 5% aqueous sodium hydroxide solution is added to 100 parts of (X′-12), and the temperature is adjusted to 40 ° C. using a TK homomixer (manufactured by Tokushu Kika) for 10 minutes at a rotational speed of 12,000 rpm. After mixing and dissolving the coating derived from [fine particle dispersion W8] adhering to the surface, it was filtered and dried at 40 ° C. for 18 hours to reduce the volatile content to 0.5% or less, and the resin particles (D '-12) was obtained.

Comparative Example 3
Place 48 parts of [resin solution 1], 12 parts of [resin solution 2], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1] in a beaker at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of [fine particle dispersion W1], 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (“ELEMINOL MON-7” manufactured by Sanyo Chemical Industries) ) 10 parts was added and dissolved uniformly. Otherwise, in the same manner as in Example 2, an aqueous dispersion (X′-13) of resin particles in which resin particles derived from [fine particle dispersion W1] attached to the surface were formed into a film was obtained. Next, 100 parts of 0.5% sodium hydroxide aqueous solution is added to 100 parts of (X′-13), and the temperature is adjusted to 40 ° C. using a TK homomixer (manufactured by Tokushu Kika) at a rotational speed of 12,000 rpm. After mixing for 10 minutes to dissolve the coating derived from [fine particle dispersion W1] adhering to the surface, it is filtered and dried at 40 ° C. for 18 hours to reduce the volatile content to 0.5% or less. (D′-13) was obtained.

Comparative Example 4
Place 48 parts of [resin solution 1], 12 parts of [resin solution 2], 27 parts of [wax dispersion 1] and 10 parts of [colorant dispersion 1] in a beaker at 25 ° C. with a TK homomixer. The mixture was stirred at 8,000 rpm and uniformly dissolved and dispersed to obtain [resin solution 1A].
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of [fine particle dispersion W6], 1 part of sodium carboxymethyl cellulose, and 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ELEMINOL MON-7”) ) 10 parts was added and dissolved uniformly. Otherwise, in the same manner as in Example 2, an aqueous dispersion (X′-14) of resin particles in which resin particles derived from [fine particle dispersion W6] attached to the surface were formed into a film was obtained. Next, 100 parts of 30% aqueous sodium hydroxide solution is added to 100 parts of (X′-14), and the temperature is adjusted to 40 ° C. using a TK homomixer (made by Tokushu Kika) for 10 minutes at 12,000 rpm. After mixing and dissolving the coating derived from [fine particle dispersion W6] adhering to the surface, it was filtered and dried at 40 ° C. for 18 hours to reduce the volatile content to 0.5% or less to obtain resin particles (D '-14) was obtained.

Example of measuring physical properties Resin particles (D-1) to (D-10) obtained in Examples 1 to 10 and Comparative Examples 1 to 4, and comparative resin particles (D'-11) to (D'-14) were used. After dispersing in water, the particle size distribution was measured with a Coulter counter. Further, the average circularity, charging characteristics, heat-resistant storage stability, and low-temperature fixability of the resin particles were measured. The results are shown in Table 1.

The average circularity is measured by the method described above.
Measuring methods of charging characteristics, heat-resistant storage stability, low-temperature fixability, and surface smoothness are as follows.

[Charging characteristics] (Charge amount)
In a 50 cc glass bottle with a stopper, 0.5 g of resin particles and 10 g of iron powder (“F-150” manufactured by Nippon Iron Powder Co., Ltd.) are precisely weighed, stoppered and placed in an atmosphere of 23 ° C. and 50% RH. Set in a turbula shaker mixer (manufactured by Willy a Baschofen) and stir for 2 minutes at 90 rpm. 0.2 g of the mixed powder after stirring was loaded into a blow-off powder charge measuring device (TB-203 manufactured by Kyocera Chemical Co., Ltd.) in which a 20 μm stainless steel wire mesh was set, under the conditions of a blow pressure of 10 KPa and a suction pressure of 5 KPa. Then, the charge amount of the residual iron powder is measured, and the charge amount of the resin particles is calculated by a conventional method. For toners, the higher the negative charge amount, the better the charging characteristics.

[Heat resistant storage stability]
Resin particles were allowed to stand for 15 hours in a dryer controlled to 50 ° C., and evaluated according to the following criteria based on the degree of blocking.
○: Blocking does not occur.
Δ: Blocking occurs, but disperses easily when force is applied.
X: Blocking occurs and does not disperse even when force is applied.

(Low temperature fixability)
After adding 1.0% Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) to the resin particles and mixing well, the powder is uniformly placed on the paper surface at 0.6 mg / cm ² (at this time the powder As a method for placing the body on the paper surface, a printer from which the heat fixing machine is removed is used (other methods may be used as long as the powder can be placed uniformly at the above-mentioned weight density). The temperature at which cold offset was generated when passing through a roller under conditions of a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ² was measured.

[Surface smoothness]
Using a scanning electron microscope (SEM), the surface of the resin particle (D) was evaluated by a photograph magnified 10,000 times and 30,000 times.
A: There is no unevenness on the surface, and it is very smooth.
○: Some irregular parts are observed on the surface, but there is almost no unevenness on the whole and it is smooth.
Δ: There are irregularities on the entire surface, but the particulate matter derived from the resin (a) cannot be confirmed.
X: The particle | grains which are extremely uneven | corrugated on the whole surface, or consist of resin (a) can be confirmed.

  The resin particles of the present invention obtained by the production method of the present invention have a uniform particle size and are excellent in charging characteristics, heat-resistant storage stability, etc., so that spacers for producing electronic parts such as slush molding resins, powder paints, liquid crystals, etc. It is extremely useful as standard particles for electronic measuring instruments, toners used for electrophotography, electrostatic recording, electrostatic printing, etc., various hot melt adhesives, resin particles used for other molding materials, and the like.

It is a conceptual diagram which shows the flowchart in the flow tester measurement of a resin particle.

Claims (10)

  An aqueous dispersion (W) containing resin particles (A) comprising the first resin (a) and a flocculant (E), a second resin (b) or an organic solvent solution thereof, or a resin (b) When the precursor (b0) or its organic solvent solution (O) is mixed, (O) is dispersed in (W), and (b0) or its organic solvent solution is used, A film (P) made of resin particles (A) or resin (a) on the surface of resin particles (B) obtained by reacting to form resin particles (B) made of (b) in (W) In the aqueous dispersion (X1) of the resin particles (C) to which is attached), at least a part of (A) or (P) on the surface of (C) is separated and / or dissolved and removed from (B) Or a part of the surface of (B) covered with (A) or (P) Method for producing particles obtained aqueous dispersion of (D) a (X2), further (X2) resin particles (D) removing the aqueous medium from.   At least a part of (A) or (P) is used so that the resin particle (D) has a surface coverage of 4.9% or less of the resin particles (B) by the resin particles (A) or the coating (P). The manufacturing method according to claim 1 to be removed.   Resin (a) is a resin having a softening start temperature of 40 to 270 ° C., a glass transition temperature of 20 to 250 ° C., an outflow temperature of 60 to 300 ° C., and a difference between the glass transition temperature of 0 to 130 ° C. and the outflow temperature. The manufacturing method according to claim 1 or 2.   Resin (a) is composed of vinyl acetate, (meth) acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, maleic acid dialkyl ester, fumaric acid, fumaric acid monoalkyl ester, fumaric acid dialkyl ester, The production method according to any one of claims 1 to 3, which is a resin containing at least one selected from alkyl (meth) acrylates having 5 to 27 carbon atoms and aliphatic vinyl hydrocarbons having 2 to 4 carbon atoms.   The method according to any one of claims 1 to 4, wherein the flocculant (E) is at least one salt selected from alkali metal salts, alkaline earth metal salts and aluminum salts of inorganic acids.   The production method according to any one of claims 1 to 5, wherein the content of the flocculant (E) in the aqueous dispersion (X1) is 0.001 to 20% by weight.   The production method according to any one of claims 1 to 6, wherein the amount of the surfactant (s) contained in the aqueous dispersion (X1) is 1000 ppm or less. Resin particles obtained by the method according to claim 1 and having a BET specific surface area of 0.5 to 5.0 m ² / g.   The resin particle according to claim 8, wherein the surface average center line roughness Ra is 0.01 to 1.0 μm.   The slush molding resin, powder paint, electronic component manufacturing spacer, standard particles for electronic measuring equipment, electrophotographic toner, electrostatic recording toner, electrostatic printing toner or hot melt adhesive. Resin particles.

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