JP2012113167A - Liquid developer for electrophotography - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid developer for electrophotography having excellent heat-resistant storage stability and uniform particle diameter and shape of resin particles included in the developer.SOLUTION: The liquid developer for electrophotography comprises core-shell type resin particles (C) dispersed in a non-aqueous organic solvent (L) having a relative permittivity of 1 to 4 at 20°C in the presence of a block copolymer (Z). The resin particles (C) comprise at least one layer of a shell layer (P) in a coating film state containing a first resin (a), and a single layer of a core layer (Q) containing a second resin (b), in which a weight ratio of (P) to (Q) ranges from (1:99) to (70:30). The block copolymer (Z) includes a structural unit (1) expressed by general formula (I) and a structural unit (2) expressed by general formula (II), in which an amino group possessed by the structural unit (1) and an organic phosphoric acid compound expressed by general formula (III) form a salt.

Description

  The present invention relates to an electrophotographic liquid developer.

  As a liquid developer for electrophotography with uniform particle size and shape of resin particles and excellent thermal characteristics, chemical stability, etc., the resin is melted in advance and further heated above the softening point of the resin. In addition, an electrophotographic liquid developer obtained by dispersing in a nonpolar medium by mechanical stirring and then cooling has been proposed (Patent Document 1). However, in the method described in Patent Document 1, since the viscosity of the molten resin is not sufficiently lowered and the resin particles are not refined, the particle size distribution of the obtained resin particles may not be sharp. Moreover, it cannot be said that the colorant etc. which are contained in the resin particle are exposed on the surface of the resin particle, and the performance of the resin (heat resistant storage stability etc.) can be sufficiently exhibited.

JP 09-179354 A

  An object of the present invention is to provide an electrophotographic liquid developer that is excellent in heat-resistant storage stability and has a uniform particle size and shape of resin particles contained therein.

式（Ｉ）〜（III）中、Ｒ^１は水素原子又はメチル基；Ｒ^２及びＲ^３は、それぞれ独立に水素原子又は炭素数１〜８のアルキル基；Ａは炭素数１〜８のアルキレン基、−[ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ]x−ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−又は−[（ＣＨ_２）ｙ−Ｏ]ｚ−（ＣＨ_２）ｙ−で表される基；Ｒ^４は炭素数１〜１８のアルキル基、ベンジル基、フェニル基、ビフェニル基、−[ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ]ｘ−Ｒ^８又は−[（ＣＨ_２）ｙ−Ｏ]ｚ−Ｒ^８で表される基であり、Ｒ^６及びＲ^７は、それぞれ独立に水素原子又はメチル基であり、Ｒ^８は水素原子、炭素数１〜１８のアルキル基、ベンジル基、フェニル基、ビフェニル基、−ＣＨＯ、−ＣＨ_２ＣＨＯ又は−ＣＨ_２ＣＯＯＲ^１２で表される基であり、Ｒ^１２は水素原子又は炭素数が１〜５のアルキル基；Ｒ^５及びＲ^５’は、それぞれ独立に水素原子、水酸基、炭素数１〜１８のアルキル基、ベンジル基、フェニル基、ビフェニル基、−[ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ]ａ−Ｒ^１１又は−[（ＣＨ_２）ｂ−Ｏ]ｃ−Ｒ^１１で表される基であり、Ｒ^９及びＲ^１０は、それぞれ独立に水素原子又はメチル基であり、Ｒ^１１は水素原子、炭素数１〜１８のアルキル基、ベンジル基、フェニル基、ビフェニル基、−ＣＨＯ、−ＣＨ_２ＣＨＯ又は−ＣＨ_２ＣＯＯＲ^１３で表される基であり、Ｒ^１３は水素原子又は炭素数が１〜５のアルキル基；ｘ、ｚ、ａ及びｃは、それぞれ独立に１〜１８の整数；ｙ及びｂは、それぞれ独立に１〜５の整数；ｍ及びｎは、それぞれ独立に１〜２００の整数を表す。
（２）２０℃における比誘電率が１〜４の非水性有機溶剤（Ｌ）中に、ブロック共重合体（Ｚ）の存在下、第１の樹脂（ａ）を含有する樹脂粒子（Ａ）が分散されてなる非水系樹脂分散液（Ｗ）と、溶解度パラメータ（以下、ＳＰ値と略記する。計算方法はＰｏｌｙｍｅｒ Ｅｎｇｉｎｅｅｒｉｎｇ ａｎｄ Ｓｃｉｅｎｃｅ，Ｆｅｂｕｒｕａｒｙ，１９７４，Ｖｏｌ．１４、Ｎｏ．２ Ｐ．１４７〜１５４による。）が８．５〜２０である有機溶剤（Ｍ）中に第２の樹脂（ｂ）が溶解された溶剤溶液（Ｏ１）又は（Ｍ）中に樹脂（ｂ）の前駆体（ｂ０）が溶解された溶剤溶液（Ｏ２）とを混合し、（Ｗ）中に（Ｏ１）又は（Ｏ２）を分散し、（Ｏ２）を用いる場合には、更に（ｂ０）を反応させて、（Ｗ）中で（ｂ）を含有する樹脂粒子（Ｂ）を形成させることにより、樹脂粒子（Ｂ）の表面に樹脂粒子（Ａ）が付着した構造の樹脂粒子（Ｄ）の非水系樹脂分散液（Ｘ１）を得て、更に（Ｘ１）から（Ｍ）を留去し、（Ａ）を被膜化して、（Ｂ）で構成されるコア層（Ｑ）の表面に（Ａ）が被膜化されたシェル層（Ｐ）が形成されて得られた樹脂粒子（Ｃ）が分散された電子写真用液体現像液の製造方法。 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 is the following two inventions.
(1) It is composed of one or more film-like shell layers (P) containing the first resin (a) and one core layer (Q) containing the second resin (b). The core-shell type resin particles (C) having a weight ratio of (P) and (Q) of (1:99) to (70:30) are structural units (1) represented by the following general formula (I): A structural unit (2) represented by the following general formula (II), an amino group possessed by the structural unit (1), and an organic phosphate compound represented by the following general formula (III): An electrophotographic liquid developer dispersed in a non-aqueous organic solvent (L) having a relative dielectric constant of 1 to 4 at 20 ° C. in the presence of a block copolymer (Z) in which a salt forms.

In formulas (I) to (III), R ¹ is a hydrogen atom or a methyl group; R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; A is an alkylene having 1 to 8 carbon atoms; ^{group, - [CH (R 6)} -CH (R 7) -O] x-CH (R 6) -CH (R 7) - or _{- [(CH 2) y-} O] z- (CH 2) y A group represented by-; R ⁴ represents an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group,-[CH (R ⁶ ) -CH (R ⁷ ) -O] x-R ⁸ or- [(CH ₂ ) y —O] z—R ⁸ , wherein R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom having 1 to 18 carbon atoms. alkyl group, a benzyl group, a phenyl group, a biphenyl group, -CHO, a group represented by _-CH 2 CHO or _-CH 2 COOR ^{12, R 1} Hydrogen atom or 1 to 5 alkyl groups of carbon number; R ⁵ and R ^{5 'are} each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, - [ A group represented by CH (R ⁹ ) —CH (R ¹⁰ ) —O] a—R ¹¹ or — [(CH ₂ ) b—O] c—R ¹¹ , wherein R ⁹ and R ¹⁰ are each independently R ¹¹ is represented by a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ^13. R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; x, z, a and c are each independently an integer of 1 to 18; y and b are each independently 1 to 5 Integer; m and n each independently represents an integer of 1 to 200 .
(2) Resin particles (A) containing the first resin (a) in the presence of the block copolymer (Z) in the nonaqueous organic solvent (L) having a relative dielectric constant of 1 to 4 at 20 ° C. Non-aqueous resin dispersion (W) in which is dissolved, and solubility parameter (hereinafter abbreviated as SP value. The calculation method is Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147-154. Is a solvent solution (O1) in which the second resin (b) is dissolved in an organic solvent (M) having a molecular weight of 8.5 to 20, or a precursor (b0) of the resin (b) in (M) When (O1) or (O2) is dispersed in (W) and (O2) is used, (b0) is further reacted and (W0) is reacted. ) Resin particles (B) containing (b) By forming, a non-aqueous resin dispersion (X1) of the resin particles (D) having a structure in which the resin particles (A) are adhered to the surfaces of the resin particles (B) is obtained, and (X1) to (M) are further obtained. Resin particles obtained by distilling off, forming (A) into a film, and forming a shell layer (P) in which (A) is formed on the surface of the core layer (Q) composed of (B) ( A method for producing an electrophotographic liquid developer in which C) is dispersed.

The electrophotographic liquid developer of the present invention has the following effects.
1. The particle size and shape of the resin particles contained are uniform.
2. Excellent heat-resistant storage stability and fluidity.

The resin (a) may be a thermoplastic resin or a thermosetting resin. Examples of the resin (a) include a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, a polyamide resin, a polyimide resin, and a silicon resin. Resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins and the like may be used, and two or more of these may be used in combination.
Among the resins (a), a vinyl resin, a polyester resin, a polyurethane resin, an epoxy resin, and a combination thereof are preferable from the viewpoint that a non-aqueous resin dispersion of fine spherical resin particles is easily obtained, and a molecular chain (k More preferably, the vinyl resin is a (co) polymer of a vinyl monomer (m) having a molecular chain (k) and, if necessary, another vinyl monomer, and the vinyl. It is another resin (composite resin) having a (co) polymer skeleton. In the case of other resins, for example, after synthesizing a vinyl (co) polymer of a vinyl monomer having a functional group such as a hydroxyl group, a carboxyl group and an amino group and a vinyl monomer (m) having a molecular chain (k), an ester It can be obtained by performing a reaction such as oxidization, amidation or urethanization.
In the present invention, the (co) polymer means a homopolymer or copolymer of monomers.

Hereinafter, the vinyl resin which is a preferable resin as the resin (a) will be described in detail.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer, and as described above, a vinyl monomer having a molecular chain (k) having an SP value difference of 2 or less from the non-aqueous organic solvent (L) ( (Co) polymers of m) and, if necessary, other vinyl monomers are preferred.

  Although it does not specifically limit as a vinyl monomer (m) which has molecular chain (k) in a side chain, The following monomers (m1)-(m4) etc. are mentioned, You may use these 2 or more types together.

(M1) Vinyl monomer having a linear hydrocarbon chain having 12 to 27 carbon atoms (preferably 16 to 25 carbon atoms) in the side chain:
Examples include unsaturated monocarboxylic acids and mono-linear alkyl (alkyl 12-27 alkyl) esters of unsaturated dicarboxylic acids. Examples of the unsaturated monocarboxylic acids and unsaturated dicarboxylic acids include (meth) acrylic. Examples thereof include carboxyl group-containing vinyl monomers having 3 to 24 carbon atoms such as acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and citraconic acid. In addition, the said (meth) acrylic acid means acrylic acid and / or methacrylic acid, and the same description is used hereafter.
Specific examples include stearyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate and (meth). Examples include eicosyl acrylate.

(M2) Vinyl monomer having a branched hydrocarbon chain having 12 to 27 carbon atoms (preferably 16 to 25 carbon atoms) in the side chain:
Unsaturated monocarboxylic acid, mono-branched alkyl (alkyl C12-27) ester of unsaturated dicarboxylic acid, etc. are mentioned. The unsaturated monocarboxylic acid and unsaturated dicarboxylic acid are the same as (m1) Things.
Specific examples include 2-decyltetradecyl (meth) acrylate.

(M3) Vinyl monomer having a polydimethylsiloxane chain in the side chain:
Examples include (meth) acryl-modified silicone represented by the following general formula.
_{CH 2 = CHR-COO-Si} (CH 3) 2 - ((CH 3) 2 SiO) m-O-Si (CH 3) 3
(In the formula, R represents a hydrogen atom or a methyl group, and m is an average value of 15 to 45.)
Specific examples include X-22-174DX, X-22-2426 and X-22-2475 [all manufactured by Shin-Etsu Silicone Co., Ltd.].

(M4) Vinyl monomer having a fluoroalkyl chain having 4 to 20 carbon atoms in the side chain:
Examples include perfluoroalkyl (alkyl) (meth) acrylic acid esters represented by the following general formula.
_{CH 2 = CR-COO- (CH} 2) p- (CF 3) q-Z
(In the formula, R represents a hydrogen atom or a methyl group, p is an integer of 0 to 3, q is any one of 2, 4, 6, 8, 10, and 12, and Z is a hydrogen atom or a fluorine atom. Represents.)
Specific examples include [(2-perfluoroethyl) ethyl] (meth) acrylic acid ester, [(2-perfluorobutyl) ethyl] (meth) acrylic acid ester, [(2-perfluorohexyl) ethyl] ( (Meth) acrylic acid ester, [(2-perfluorooctyl) ethyl] (meth) acrylic acid ester, [(2-perfluorodecyl) ethyl] (meth) acrylic acid ester, and [(2-perfluorododecyl) ethyl ] (Meth) acrylic acid ester etc. are mentioned.
Preferred among (m1) to (m4) are (m1), (m2) and (m3), and more preferred is the combined use of (m1) and (m2).

  Examples of the vinyl monomer other than the vinyl monomer (m) having the molecular chain (k) in the side chain include the following (1) to (10), and two or more of these may be used in combination.

(1) Vinyl hydrocarbon:
(1-1) Aliphatic vinyl hydrocarbons: alkenes (for example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene and other α-olefins); alkadienes (for example, butadiene) , Isoprene, 1,4-pentadiene, 1,6-hexadiene and 1,7-octadiene).
(1-2) Cycloaliphatic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes (such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene and ethylidenebicycloheptene); terpenes (such as pinene, limonene and Inden, etc.).
(1-3) Aromatic vinyl hydrocarbon: Styrene or its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitution product (for example, 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, and trivinyl benzene); and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomer and metal salt thereof:
C3-C30 unsaturated monocarboxylic acid, unsaturated dicarboxylic acid or its anhydride and its monoalkyl (C1-C11 of alkyl group) ester [For example, (meth) acrylic acid, (anhydrous) maleic acid, fumar Carboxyl group-containing vinyl monomers such as acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, maleic acid monomethyl ester, fumaric acid monoethyl ester and itaconic acid monobutyl ester].

  (3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesterified products and salts thereof: Alkene sulfonic acids having 2 to 14 carbon atoms [for example, vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid, etc. And alkyl derivatives thereof having 2 to 24 carbon atoms (for example, α-methylstyrenesulfonic acid); sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide {for example, 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- (meth) Chloramido-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid, poly (n = 2 to 30) oxyalkylene (oxyethylene, oxy Propylene and oxybutylene, etc .: may be single, random or block) Mono (meth) acrylate sulfate ester [poly (n = 5-15) oxypropylene monomethacrylate sulfate ester, etc.], polyoxyethylene polycyclic phenyl ether sulfate ester, And sulfate esters or sulfonic acid group-containing monomers represented by the following general formulas (1-1) to (1-3)}; and salts thereof.

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

CH = CH-CH ₃
｜
R'-Ar-O- (AO) n SO 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 and R ′ are each independently an alkyl group having 1 to 15 carbon atoms; AO is an oxyalkylene group having 2 to 4 carbon atoms, and AO may be used alone or in combination of two or more. When a species or more is used in combination, the bonding form may be random or block; m and n are each independently a number of 1 to 50; Ar is a benzene ring; R ″ is the number of carbons that may be substituted with a fluorine atom 1-15 alkyl groups are represented.

(4) Phosphoric acid group-containing vinyl monomer and salt thereof:
(Meth) acryloyloxyalkyl (carbon number 1 to 24) phosphoric acid monoester [for example, 2-hydroxyethyl (meth) acryloyl phosphate and phenyl-2-acryloyloxyethyl phosphate, etc.]; (meth) acryloyloxyalkyl (carbon number) 1-24) Phosphonic acids (for example, 2-acryloyloxyethylphosphonic acid, etc.).

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.
Of these, 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-vinyl Thiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof (6-2) Ami Group-containing vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic acid Amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone, etc. (6-3) Nitrile group-containing vinyl monomer: (meth) acrylonitrile, Cyanostyrene, cyanoacrylate, etc. (6-4) Quaternary ammonium cation group-containing vinyl monomer: Tertiary amine group-containing vinyl monomer [for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, Methylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine, etc.] (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate), etc. (6-5) Nitro group-containing vinyl monomer: nitrostyrene, etc. (6-6) Urethane group-containing vinyl monomer: equimolar amount of hydroxyethyl (meth) acrylate and monofunctional isocyanate compound (phenyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, etc.) Reaction product, hydroxyethyl (meth) acrylate and polyalkylene glycol chain (2 to 4 carbon atoms of alkylene group) and bifunctional isocyanate compound (isophorone diisocyanate, hexyl diisocyanate) Over preparative and equimolar reaction products of tolylene Ishia sulfonate, etc.)

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

(8) Halogen element-containing vinyl monomers other than fluorine:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, chloroprene, etc.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl ester {for example, vinyl acetate, vinyl butyrate, 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-ethoxy acrylate, (meth) acrylic acid alkyl ester having 1 to 11 carbon atoms (straight chain or branched chain) [methyl (meth) acrylate , Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate], dialkyl fumarate (dialkyl fumarate) 2 alkyl groups are straight chain, branched chain or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (dialkyl maleate) (2 alkyl groups are 2 to 2 carbon atoms) 8 linear, branched or alicyclic groups), poly (meth) allyloxyalkanes (diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxy) Vinyl monomers having a polyalkylene glycol chain, such as butane and tetrametaallyloxyethane, etc. {polyethylene glycol [number average molecular weight (hereinafter abbreviated as Mn) 300] mono (meth) acrylate, polypropylene glycol (Mn = 500) mono Acrylate, methyl alcohol ethylene oxide (hereinafter abbreviated as EO) Adduct (meth) acrylate and lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.]}
(9-2) Vinyl (thio) ether (for example, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro-1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl-2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, etc.)
(9-3) Vinyl ketones (for example, vinyl methyl ketone, vinyl ethyl ketone and vinyl phenyl ketone); vinyl sulfones (for example, divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone and divinyl sulfone) Side etc.)

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

  Of these vinyl monomers other than these vinyl monomers (m), a vinyl ester such as a (meth) acrylic acid alkyl ester having a C1-C11 alkyl group and a vinyl monomer having a polyalkylene glycol chain, Of these, a carboxyl group-containing vinyl monomer, a sulfone group-containing vinyl monomer, an amino group-containing vinyl monomer, and a urethane group-containing vinyl monomer, and more preferable are (meth) acrylic acid alkyl esters having an alkyl group having 1 to 11 carbon atoms. Then, methyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, and among vinyl monomers having a polyalkylene glycol chain, (meth) acrylic acid polyethylene glycol ester {" BLEMMER PE-3 0 ”[manufactured by NOF Corporation], etc., among the carboxyl group-containing vinyl monomers are (meth) acrylic acid, crotonic acid, itaconic acid and maleic acid, and among the sulfone group-containing vinyl monomers, Alkyl (C3-C18) allylsulfosuccinic acid {"Eleminol JS-2" [manufactured by Sanyo Chemical Industries, Ltd.] etc.] and poly (n = 2-30) oxyalkylene (oxyethylene, oxypropylene, oxybutylene, etc.) : Single, random, or block) mono (meth) acrylate sulfate {"Eleminol RS-30" (manufactured by Sanyo Chemical Industries, Ltd.] etc.), and among amino group-containing vinyl monomers, aminoethyl ( With (meth) acrylate, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate Ri, in the urethane group-containing vinyl monomer is an equimolar reaction product of hydroxyethyl (meth) acrylate and phenyl isocyanate.

Specific examples of vinyl resins include (meth) acrylic acid ester- (meth) acrylic acid perfluoroalkyl ester, (meth) acrylic modified silicone- (meth) acrylic acid ester, vinyl acetate- ( (Meth) acrylic acid- (meth) acrylic acid perfluoroalkyl ester, (meth) acrylic acid ester- (meth) acrylic acid perfluoroalkyl ester, (meth) acrylic acid alkyl (straight and / or branched) ester- ( (Meth) acrylic acid, vinyl acetate- (meth) acrylic acid- (meth) acrylic acid ester, (meth) alkyl acrylate (linear and / or branched) ester- (meth) acrylic acid polyethylene glycol ester, (meth) Alkyl acrylate (straight and / or branched) ester- (meth ) Acrylic acid- (meth) acrylic acid polyethylene glycol ester, alkyl (meth) acrylate (linear and / or branched) ester-diethylaminoethyl (meth) acrylate- (meth) acrylic acid polyethylene glycol ester, (meth) acrylic Acid alkyl (linear and / or branched) ester- (meth) acrylic acid-diethylaminoethyl (meth) acrylate- (meth) acrylic acid polyethylene glycol ester, alkyl (meth) acrylate (linear and / or branched) Ester- (meth) acrylic acid polyethylene glycol ester-equimolar reaction product of hydroxyethyl (meth) acrylate and phenyl isocyanate, alkyl (meth) acrylate (linear and / or branched) ester- (meth) acrylic acid-hydroxy Equimolar reaction product of chill (meth) acrylate and phenyl isocyanate, alkyl (meth) acrylate (linear and / or branched) ester- (meth) acrylic acid- (meth) acrylic acid polyethylene glycol ester-hydroxyethyl (meta ) An equimolar reaction product of acrylate and phenyl isocyanate, a salt of a copolymer of these monomers, and the like.
Of these, preferred are alkyl (meth) acrylate (linear and / or branched) ester- (meth) acrylic acid- (meth) acrylic acid polyethylene glycol ester, alkyl (meth) acrylate (linear and / or). Or branched) ester- (meth) acrylic acid-diethylaminoethyl (meth) acrylate- (meth) acrylic acid polyethylene glycol ester, alkyl (meth) acrylate (straight and / or branched) ester- (meth) acrylic acid Polyethylene glycol ester, alkyl (meth) acrylate (linear and / or branched) ester-diethylaminoethyl (meth) acrylate- (meth) acrylic acid polyethylene glycol ester, alkyl (meth) acrylate (linear and / or branched) Chain) Ester- (Meth) acrylic Polyethylene glycol ester-equimolar reaction product of hydroxyethyl (meth) acrylate and phenyl isocyanate, and alkyl (meth) acrylate (linear and / or branched) ester-(meth) acrylic acid-(meth) acrylic acid polyethylene glycol It is an equimolar reaction product of ester-hydroxyethyl (meth) acrylate and phenyl isocyanate.
In addition, the same thing is mentioned about the composition of the vinyl (co) polymer frame | skeleton in other resin which has a vinyl (co) polymer frame | skeleton, A preferable thing is also the same.

Molecular chain having an SP value difference of 2 or less from the non-aqueous organic solvent (L) in the vinyl monomer constituting the vinyl polymer skeleton in the resin other than the vinyl resin or vinyl resin having a vinyl polymer skeleton (k The content of the vinyl monomer (m) having) is preferably 10% by weight or more, more preferably 10 to 90% by weight, particularly preferably 15 to 80% by weight, and most preferably 20 to 60% by weight. .
With such a content, when the resin (a) forms the resin particles (A) with the non-aqueous resin dispersion, the organic solvent (L) is used at least under the conditions for forming the non-aqueous resin dispersion (W). ) To 1% by weight or less, and the resin particles (C) are difficult to unite.

  Resin (a) is a (co) polymer skeleton of a vinyl monomer (m) having a molecular chain (k) whose SP value difference with the non-aqueous organic solvent (L) is 2 or less and, if necessary, another vinyl monomer And (m) is a vinyl monomer (m1) having a linear hydrocarbon chain having 12 to 27 carbon atoms and a vinyl monomer (m2) having a branched hydrocarbon chain having 12 to 27 carbon atoms The weight ratio of (m1) and (m2) is (m1) :( m2), preferably 90:10 to 10:90, and more preferably 80, from the viewpoint of the particle size and fixing property of the resin particles. : 20 to 20:80, particularly preferably 70:30 to 30:70.

Resin (a) has a (co) polymer skeleton of vinyl monomer (m) and optionally other vinyl monomers, and (m) is a vinyl monomer (m3) having a polydimethylsiloxane chain and / or carbon number. When the vinyl monomer (m4) having 4 to 20 fluoroalkyl chains is contained, from the viewpoint of dispersion stability of the resin particles (C), the following surface composition ratio of (C) is preferably 0.75 to 0. 98, more preferably 0.80 to 0.95, and particularly preferably 0.83 to 0.92. Within this range, the affinity of (C) for (L) is improved and the dispersion stability is improved. The surface composition ratio can be adjusted by adjusting the content of (m3) and / or (m4), for example.
The surface composition ratio is calculated by (C + Si + F) / (C + Si + F + O) based on the element strength derived from carbon atom, silicon atom, fluorine atom and oxygen atom measured under the following conditions using X-ray photoelectron analysis.
Device (example): “ESCA5400” (manufactured by ULVAC-PHI)
X-ray source: Mg (no monochromator)
Output: 15KV, 400W
Measurement area: 1.1mmφ

The resin (a) has a solubility in the non-aqueous organic solvent (L) of preferably 1% by weight or less, and more preferably 0.5% by weight or less. If the solubility of (a) is 1% by weight or less, it becomes difficult for the resin particles (C) to coalesce.
In the present invention, the solubility of (a) in (L) is the weight of the supernatant obtained by dissolving (a) in (L) until saturation is reached, and precipitating the insoluble matter by centrifugation. Further, the value is obtained by dividing the weight of the residue after drying at the boiling point of (L) with a vacuum dryer.
Specifically, it is calculated by the following procedure.
The saturated solution (25 ° C.) containing the insoluble content of the resin (a) is centrifuged for 30 minutes under the condition of 10,000 ppm, and about 2 g (yg) of the supernatant is collected in an aluminum container. Further, the supernatant is dried with a vacuum dryer under a reduced pressure of 20 mmHg for 1 hour under the temperature condition of the boiling point (L), and the weight of the residue is weighed. If the residue weight at this time is Yg, the solubility of (a) in (L) can be calculated by Y / y × 100 (% by weight).

The resin (a) has a molecular chain (k) having a high affinity with the non-aqueous organic solvent (L) in the side chain in order to obtain a non-aqueous resin dispersion (W) of fine spherical resin particles (A). A resin is preferred.
When the SP value difference between (L) and (k) is 2 or less (preferably 1 or less), (k) is considered to have high affinity with (L).
Specific examples of the molecular chain (k) include a straight hydrocarbon chain having 12 to 27 carbon atoms (preferably 16 to 25), a branched hydrocarbon chain having 12 to 27 carbon atoms (preferably 16 to 25), Examples thereof include a polydimethylsiloxane chain and a fluoroalkyl chain having 4 to 20 carbon atoms. From the viewpoint of ease of synthesis, a linear hydrocarbon chain having 12 to 27 carbon atoms and a branched chain having 12 to 27 carbon atoms are preferable. A hydrocarbon chain and a polydimethylsiloxane chain are more preferable, and a combination of a linear hydrocarbon chain having 12 to 27 carbon atoms and a branched hydrocarbon chain having 12 to 27 carbon atoms is more preferable. The linear hydrocarbon chain having 12 to 27 carbon atoms preferably has crystallinity.
The content of the molecular chain (k) in the resin (a) is preferably 10 to 90% by weight, more preferably 15 to 80% by weight, and particularly preferably 20 to 60% by weight.

  From the viewpoint of reducing dissolution or swelling of the resin particles (A) in the solvent used at the time of dispersion, the molecular weight, SP value, crystallinity, molecular weight between cross-linking points, etc. of the resin (a) are appropriately adjusted. It is preferable to do this.

  The Mn (measured by gel permeation chromatography) of the resin (a) is preferably 1 to 5 million, more preferably 2 to 5 million, and particularly preferably 500 to 500,000. The SP value is preferably 7-18, and more preferably 8-14.

In the present invention, Mn and weight average molecular weight (hereinafter abbreviated as Mw) of a resin other than polyurethane resin such as vinyl resin are as follows using tetrahydrofuran (THF) soluble content by gel permeation chromatography (GPC). Measured under the following conditions.
Apparatus (example): HLC-8120 [manufactured by Tosoh Corporation]
Column (example): TSKgelGMHXL (2)
TSKgelMultiporeHXL-M (1 pc.)
Sample solution: 0.25 wt% THF solution Injection volume: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (Molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400) , 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]
Moreover, Mn and Mw of a polyurethane resin are measured on condition of the following using GPC.
Apparatus (example): HLC-8220GPC [manufactured by Tosoh Corporation]
Column (example): Guardcolumn α
TSKgelα-M
Sample solution: 0.125 wt% dimethylformamide solution Solution injection volume: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (Molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400) , 190,000, 355,000, 1,090,000, 2,890,000)

  The melting point of the resin (a) is preferably 0 ° C. or higher, more preferably 30 to from the viewpoint of the particle size uniformity, powder flowability, heat resistance during storage and stress resistance of the resin particles (C). 200 ° C.

The glass transition temperature (hereinafter abbreviated as Tg) of the resin (a) is preferably 10 from the viewpoint of the particle size uniformity, powder flowability, heat resistance during storage and stress resistance of the resin particles (C). It is -250 degreeC, More preferably, it is 20-230 degreeC, Especially preferably, it is 30-200 degreeC, Most preferably, it is 40-100 degreeC. If the Tg is lower than the temperature at which the non-aqueous resin dispersion (X1) is produced, the effect of preventing coalescence or preventing splitting is reduced, and the effect of increasing the uniformity of particle size is reduced.
Moreover, Tg of shell layer (P) containing resin (a) becomes like this. Preferably it is 10-200 degreeC, More preferably, it is 20-100 degreeC, Most preferably, it is 30-85 degreeC.
In addition, melting | fusing point and Tg in this invention are the values calculated | required from DSC measurement or a flow tester measurement (when it cannot measure by DSC).

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

As the second resin (b) used in the present invention, any resin can be used as long as it is a known resin, and specific examples thereof include those similar to the resin (a). As the resin (b), a preferable one can be appropriately selected according to the use and purpose.
In general, the resin (b) is preferably a polyester resin, a polyurethane resin, an epoxy resin, a vinyl resin, and a combination thereof, more preferably a polyurethane resin and a polyester resin, and particularly preferably 1, 2 -Polyester resin and polyurethane resin containing propylene glycol as a structural unit.
Hereinafter, vinyl resin, polyester resin, polyurethane resin, and epoxy resin which are preferable resins as the resin (b) will be described.

As a vinyl resin, the thing similar to what was illustrated as a vinyl resin used for resin (a) is mentioned. However, the structural unit of the vinyl monomer (m) having the molecular chain (k) may or may not be included.
Specific examples of the vinyl monomer copolymer used for the resin (b) 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 copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid-divinylbenzene copolymer, Examples thereof include styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymers and salts of these copolymers.

Examples of the polyester resin include polycondensates of polyols with polycarboxylic acids, acid anhydrides or lower alkyl esters thereof, and metal salts of these polycondensates. As the polyol, the diol (11) and the trivalent to octavalent or higher polyol (12) are polycarboxylic acids, their acid anhydrides or their lower alkyl esters, and the dicarboxylic acid (13), the trivalent to hexavalent or More polycarboxylic acids (14) and their 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 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. / 1 to 1/4, particularly preferably 1 / 1.3 to 1/3.
In order to keep the carboxyl group content within the above-mentioned preferred range, a polyester having an excessive hydroxyl group may be treated with a 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, tetradecandiol, neopentyl glycol and 2,2-diethyl-1,3-propanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol) , Polypropylene glycol and polytetramethylene ether glycol); alicyclic diols having 4 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); Reactive or alicyclic diol AO [EO, propylene oxide (hereinafter abbreviated as PO) and butylene oxide (hereinafter abbreviated as BO), etc.] adducts (addition mole number 1 to 120); bisphenols (bisphenol A, bisphenol) F and bisphenol S etc.) AO (EO, PO and BO etc.) adducts (addition mole number 2-30); polylactone diol (poly-ε-caprolactone diol etc.); and polybutadiene diol etc.

As the diol (11), in addition to the diol having no functional group other than the above 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.
Examples of the diol having a carboxyl group include dialkylol alkanoic acids [having 6 to 24 carbon atoms such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylol. Heptanoic acid and 2,2-dimethyloloctanoic 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 (alkyl group having 1 to 6 carbon atoms) and an AO adduct thereof (AO includes EO and PO, such as 1 to 6 added moles of AO): for example, N, N-bis (2- Hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, etc.]; and bis (2-hydroxyethyl) phosphate, and the like.
Examples of neutralized salts of diols 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).
Of these, alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof are preferable.

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 such as glycerin, Trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan and polyglycerin, etc .; sugars and derivatives thereof such as sucrose and methylglucoside, etc .; AO adducts of polyhydric aliphatic alcohols (addition mole number: 2-120) AO adducts of trisphenols (trisphenol PA and the like) (addition mole number 2 to 30); AO adducts of novolak resins (phenol novolak and cresol novolak and the like) (addition mole number 2 to 30); acrylic polyol [hydroxy Of ethyl (meth) acrylate and other vinyl monomers Polymers, etc.]; 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 (such as succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid and decylsuccinic acid) and alkenyl succinic acid (dodecenyl succinic acid, Pentadecenyl succinic acid and octadecenyl succinic acid); alicyclic dicarboxylic acid having 6 to 40 carbon atoms [dimer acid (dimerized linoleic acid) and the like], alkenedicarboxylic acid having 4 to 36 carbon atoms (maleic acid) Acid, fumaric acid, citraconic acid, etc.); C8-36 aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) and the like.
Of these, alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable.
Examples of the trivalent to hexavalent or higher polycarboxylic acid (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
In addition, as dicarboxylic acid (13) or 3-6 or higher polycarboxylic acid (14), acid anhydrides of the above or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester and isopropyl ester) Etc.) may be used.

The polyester resin used in the present invention may be one produced in the same manner as a normal polyester resin production method. For example, the reaction temperature is preferably 150 to 280 ° C. and the reaction time is preferably 30 minutes or more 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, and catalysts described in JP-A-2006-243715 [ Titanium dihydroxybis (triethanolaminate) and titanium monohydroxytris (triethanolaminates and their intramolecular polycondensates, etc.) and catalysts described in JP 2007-11307 A (titanium tributoxy terephthalate, titanium triiso Propoxy terephthalate and titanium diisopropoxy diterephthalate, etc.)}, zirconium-containing catalysts (such as zirconyl acetate, etc.) and zinc acetate.

As the polyurethane resin, polyisocyanate (15) and active hydrogen-containing compound [water, polyol {including the diol (11) [including diol (11a) having a functional group other than hydroxyl group]] and 3 to 8 or more valences Polyol (12)}, polycarboxylic acid [said dicarboxylic acid (13) and polycarboxylic acid (14) having 3 or more valences or higher], polyester polyol obtained by polycondensation of polyol and polycarboxylic acid, carbon number 6 -12 ring-opening polymer of lactone, polyamine (16), polythiol (17) and combinations thereof), and terminal isocyanate group prepolymer obtained by reacting (15) with an active hydrogen-containing compound, , Primary and / or secondary monoamine (18) in an equivalent amount with respect to the isocyanate groups of the prepolymer, Obtained by reacting, and amino group-containing polyurethane resins.
The content of carboxyl groups in the polyurethane resin is preferably 0.1 to 10% by weight.

  Examples of the diol (11), the trivalent to octavalent or higher polyol (12), the dicarboxylic acid (13), and the trivalent to hexavalent or higher polycarboxylic acid (14) include those described above, and are preferable. 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, araliphatic 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 and Oxazolidone group-containing modified products) and mixtures of two or more thereof.

Specific examples of the aromatic polyisocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- or 4, 4'-diphenylmethane diisocyanate (MDI), crude MDI {crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; trifunctional or more of diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight)] Of polyamines]: polyallyl polyisocyanate (PAPI)}, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate and m- or -p-isocyanatophenyl And sulfonyl isocyanate.
Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate Etc.
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 2,6-norbornane diisocyanate and the like.
Specific examples of the araliphatic polyisocyanate include m- or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).
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.), urethane-modified TDI and a mixture of two or more thereof (for example, modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)) And the like].
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 more preferred are TDI, MDI and HDI. Hydrogenated MDI and IPDI.

As polyamine (16), aliphatic polyamines (2-18 carbon atoms): [1] aliphatic polyamine {2-6 alkylene diamines (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine and hexamethylenediamine) Etc.), polyalkylene (2 to 6 carbon atoms) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; [2] these alkyls (C1-C4) or hydroxyalkyl (C2-C4) substituted [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2, 5- Xamethylenediamine and methyliminobispropylamine, etc.]; [3] Alicyclic or heterocyclic-containing aliphatic polyamine {3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5] , 5] undecane, etc.}; [4] Aromatic ring-containing aliphatic amines (C8-15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamines (C4-15) ): 1,3-diaminocyclohexane, isophorone diamine, mensen diamine and 4,4′-methylene dicyclohexane diamine (hydrogenated methylene dianiline), etc., heterocyclic polyamines (4 to 15 carbon atoms): piperazine, N— Aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, etc. Aromatic polyamines (6 to 20 carbon atoms): [1] unsubstituted aromatic polyamine [1,2-, 1,3- or -1,4-phenylenediamine, 2,4'- or -4,4 ' -Diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane -4,4 ', 4 "-triamine, naphthylenediamine, etc.]; [2] Nuclear-substituted alkyl groups (alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n- or isopropyl and butyl groups) Aromatic polyamines having, for example, 2,4- or 2,6-tolylenediamine, crude tolylenediamine , Diethyltolylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2,4- Diaminobenzene, 1,3-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'-tetramethyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2' -Diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl -4,4'-diaminodiphenyl ether and 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone etc.] and mixtures of these isomers in various proportions; [3] nuclear substitution electrons Aromatic polyamines having a suction group (halogen atoms such as Cl, Br, I and F; alkoxy groups such as methoxy and ethoxy; nitro groups, etc.) [methylene bis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro B-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 ( -Bromoaniline), 4,4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline and the like]; [4] aromatic polyamines having secondary amino groups {above [1] to [3 ] In which part or all of —NH ₂ of the aromatic polyamine is substituted with —NH—R ′ (where R ′ is an alkyl group such as a lower alkyl group such as a methyl group or an ethyl group)} [4, 4 ′ -Di (methylamino) diphenylmethane and 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 and polyalkylene polyamines, etc., polyether polyamines: polyether polyols Hydride of a cyanoethylated product (eg, a polyalkylene glycol).

  Examples of the polythiol (17) include alkanedithiols having 2 to 36 carbon atoms (ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.) and the like.

  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 {water, polyol [the diol (11) and a polyol having 3 to 8 or more valences (12)], The dicarboxylic acid (13), the polyvalent or trivalent or higher polycarboxylic acid (14), the polyamine (16), the polythiol (17) and the like} and the polyepoxide (19) and the dicarboxylic acid ( 13) or a cured product of a tricarboxylic acid (3) or higher polycarboxylic acid (14) with an acid anhydride.

  The polyepoxide (19) used for this invention will not be specifically limited if it has two or more epoxy groups in a molecule | numerator. The polyepoxide (19) preferably has 2 to 6 epoxy groups in the molecule from the viewpoint of the mechanical properties of the cured product. The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide (19) is preferably 65 to 1,000, more preferably 90 to 500. When the epoxy equivalent is 1,000 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.

Specific 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'-dihydroxybiphenyldi Glycidyl ether, tetramethylbiphenyl diglycidyl ether Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -T-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, phenol or By the condensation reaction of glycidyl ether of cresol novolac resin, glycidyl ether of limonenephenol 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 ether of polyphenol obtained and polyglycidyl ether of polyphenol obtained by condensation reaction of resorcin and acetone. Examples of the glycidyl ester of polyhydric phenol include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester. Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine and N, N, N ′, N′-tetraglycidyldiphenylmethanediamine. Further, in the present invention, as the aromatic system, P-aminophenol triglycidyl ether, tolylene diisocyanate or a diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, obtained by reacting a polyol with the above two reactants. Also included are diglycidyl ethers of glycidyl group-containing polyurethane (pre) polymers and alkylene oxide (such as ethylene oxide and propylene oxide) adducts of bisphenol A.
Examples of the heterocyclic polyepoxy compound include trisglycidyl melamine.
Examples of the 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-methylcyclohexylmethyl) adipate and bis (3,4-epoxy-6-methylcyclohexyl) Methyl) butylamine and dimer acid diglycidyl ester. Moreover, as an alicyclic type | system | group, the nuclear hydrogenation thing of the said aromatic polyepoxide compound is also included.
Examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Examples include diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether. It is done. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate and diglycidyl pimelate. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidyl hexamethylenediamine. In the present invention, the aliphatic type also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate.
Of the polyepoxides (19), aliphatic polyepoxy compounds and aromatic polyepoxy compounds are preferred. In addition, a polyepoxide (19) may use 2 or more types together.

What is necessary is just to adjust Mn of resin (b), melting | fusing point, Tg, and SP value suitably in a preferable range with a use.
The SP value of the resin (b) is preferably 7 to 18 (cal / cm ³ ) ^1/2 , more preferably 8 to 14 (cal / cm ³ ) ^1/2 , and particularly preferably 9 to 14 (cal / Cm ³ ) ^1/2 .
The Mn of the resin (b) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000.
The melting point of the resin (b) is preferably 20 to 300 ° C, more preferably 80 to 250 ° C.
The Tg of the resin (b) is preferably 20 to 200 ° C, more preferably 40 to 150 ° C.
The SP value of the resin (b) is preferably 8 to 16 (cal / cm ³ ) ^1/2 , and more preferably 9 to 14 (cal / cm ³ ) ^1/2 .

The liquid developer for electrophotography of the first invention is a core-shell type developer in the presence of a block copolymer (Z) in a non-aqueous organic solvent (L) having a relative dielectric constant of 1 to 4 at 20 ° C. The resin particles (C) are dispersed.
The block copolymer (Z) in the present invention has the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II), and A block copolymer in which the amino group of the structural unit (1) and the organophosphate compound represented by the general formula (III) form a salt.

In the general formula (I), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
The alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , T-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group and cyclooctyl group. Among these, a methyl group and an ethyl group are preferable.

In the general formula (I), A is an alkylene group having 1 to 8 carbon atoms, — [CH (R ⁶ ) —CH (R ⁷ ) —O] x —CH (R ⁶ ) —CH (R ⁷ ) — or — A group represented by [(CH ₂ ) y —O] z— (CH ₂ ) y —.
The alkylene group having 1 to 8 carbon atoms may be either a straight chain or branched chain, and specifically includes a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and an octylene. Groups and the like.
R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
x and z are integers of 1 to 18, preferably integers of 1 to 4, and more preferably 1 and 2. y is an integer of 1-5, preferably an integer of 1-4, more preferably 2 and 3. If x, y, and z are in the above ranges, the dispersibility can be improved.
Among A, from the viewpoint of dispersibility, an alkylene group having 1 to 8 carbon atoms is preferable, and a methylene group and an ethylene group are more preferable.

In the general formula (II), R ⁴ represents an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] x —R ^8. or - represents a _{[(CH 2) y-O} ] z-R 8. In addition, when R ⁴ has an aromatic ring, it may have an appropriate substituent on the aromatic ring, for example, a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group T-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, cyclooctyl group, n-decyl group, n-dodecyl group, cyclododecyl group, n-tetradecyl group, Examples include an n-hexadecyl group, an n-octadecyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, and a lower alkyl group-substituted adamantyl group.

R ⁸ is a group represented by a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹² . The alkyl group having 1 to 18 carbon atoms include the same as those exemplified for R ^4.
R ¹² is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms, specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group. , T-butyl group, n-pentyl group, cyclopentyl group and the like.
X, y and z in R ⁴ are in the same range as A, and the preferred range is also the same.

  The ratio m / n of the unit number m of the structural unit (1) and the unit number n of the structural unit (2) constituting the block copolymer (Z) is preferably 0.01 to 1, and more preferably 0. 0.05 to 0.5. When the ratio m / n is within the above range, the proportion of the salt-forming sites formed by the amino groups of the structural unit (1) is appropriate, and the dispersibility of the resin particles (C) becomes good.

In the block copolymer (Z), the number of units m of the structural unit (1) and the number of units n of the structural unit (2) may be integers of 1 to 200, respectively, and are not particularly limited, but m is preferable. Is 1-20, more preferably 1-10. n is preferably 20 to 100, and more preferably 30 to 70.
The Mw of the block copolymer (Z) is preferably 500 to 20,000, more preferably 1,000 to 15,000, and particularly preferably 3,000 to 12,000. By being in the said range, the dispersibility of the resin particle (C) becomes favorable.
In addition, Mw of a block copolymer (Z) can be measured by the method similar to Mn and Mw of the said resin (a).

  The block copolymer (Z) has the structural unit (1) and the structural unit (2), and the structural unit (1) is bonded to only one end of the block copolymer (Z). It is preferable from the viewpoint of dispersibility of the resin particles (C). That is, the structural unit (1) and the structural unit (2) may be combined in the order of the structural unit (1) -the structural unit (2), and the structural unit (1) -the structural unit (2). The structural unit (1) may be bonded in this order, or the structural unit (1) and the structural unit (2) may be bonded repeatedly, but in the present invention, the structural unit (1 ) -Bonded in the order of the structural unit (2) is preferred.

The organic phosphate compound that forms a salt with the amino group of the structural unit (1) of the block copolymer (Z) is a compound having a structure represented by the general formula (III).
By using the organic phosphoric acid compound, the dispersibility of the resin particles (C) is improved. In addition, an organic phosphoric acid compound may be used independently and may use 2 or more types together.

In the general formula (III), R ⁵ and R ^{5 ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁹ ) — It is a group represented by CH (R ¹⁰ ) —O] a—R ¹¹ or — [(CH ₂ ) b—O] c—R ¹¹ . When R ⁵ or R ^{5 ′} has an aromatic ring, it may have an appropriate substituent on the aromatic ring, for example, a linear or branched alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group having 1 to 18 carbon atoms are the same as those exemplified for R ⁴ .
R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a methyl group.
R ¹¹ is a hydrogen atom, a C 1-18 alkyl group, a benzyl group, a phenyl group, a biphenyl group, —CHO, —CH ₂ CHO or —CH ₂ COOR ¹³ , and R ¹³ is a hydrogen atom. Or it is a C1-C5 linear, branched or cyclic alkyl group. Examples of the alkyl group having 1 to 18 carbon atoms in R ¹¹ include the same as those exemplified for R ⁴ .
In R ⁵ and R ^{5 ′} , a and c are each independently an integer of 1 to 18, preferably an integer of 1 to 4, more preferably 1 and 2. b is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 and 3.

  The content of the organic phosphate compound in the block copolymer (Z) is preferably 0.05 to the amino group of the structural unit (1) from the viewpoint of dispersibility of the resin particles (C). It is 4.0 mol%, More preferably, it is 0.1-2.0 mol%, Most preferably, it is 0.2-1.0 mol%. In addition, when using together 2 or more types of organic phosphoric acid compounds, the content rate which totaled these should just exist in the said range.

  As a manufacturing method of a block copolymer (Z), it has the said structural unit (1), a structural unit (2), the amino group which the structural unit (1) has, and the said organic phosphate compound There is no particular limitation as long as it is a method capable of producing a salt-formed one. For example, after the structural unit (1) and the structural unit (2) are polymerized using a known polymerization method, a non-aqueous medium is used. It can be prepared by dissolving or dispersing in, then adding an organic phosphate compound in a non-aqueous medium and stirring.

  A block copolymer (Z) may be used independently and may use 2 or more types together, and the usage-amount is resin particle (C) 100 from a dispersible viewpoint of the resin particle (C). Preferably it is 5-200 weight part with respect to a weight part, More preferably, it is 10-100 mass part, Most preferably, it is 20-80 mass part.

  In the electrophotographic liquid developer of the first invention, one or more shell layers (P) in the form of a film containing the first resin (a) and one layer containing the second resin (b) In the core-shell type resin particles (C) composed of the core layer (Q), the weight ratio [(P) :( Q)] of (P) to (Q) is from (1:99) to (70). From the viewpoint of the particle size uniformity of (C) and the storage stability of the liquid developer for electrophotography, it is preferably (5:95) to (50:50), and more preferably (10). : 90-35: 65). When the weight of the shell layer (P) is too small, the blocking resistance may be lowered. Further, if the weight of the shell layer (P) is too large, the particle size uniformity may be lowered. The shell layer (P) may be formed of two or more layers (for example, 2 to 5 layers), but one layer is preferable.

The non-aqueous organic solvent (L) in which the resin particles (C) are dispersed is a solvent having a relative dielectric constant of 1 to 4 at 20 ° C. from the viewpoint of dispersion stability of (C).
Specific examples of the non-aqueous organic solvent (L) include hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E, Isopar. G, Isopar H, Isopar L (isopar: trade name of Exxon), Shellsol 70, Shellsol 71 (shellsol: trade name of Shell Oil), Amsco OMS, Amsco 460 (Commercial name of Amsco: Spirits) , Silicone oil, liquid paraffin, and the like. These may be used alone or in combination of two or more.
Of these, solvents having a boiling point of 100 ° C. or higher are preferable from the viewpoint of odor, and more preferable are hydrocarbon solvents having 10 or more carbon atoms (such as dodecane, isododecane and liquid paraffin) and silicone oil. Particularly preferred is liquid paraffin.
The dielectric constant of the non-aqueous organic solvent (L) is measured using a bridge method (JIS C2101-1999). An empty capacitance C ₀ (pF) before filling the sample and an equivalent parallel capacitance Cx (pF) at the time of filling the sample are measured, and a dielectric constant ε is calculated by the following formula (1). The relative dielectric constant is given by the ratio of ε to the relative dielectric constant of air 1.000585.
ε = Cx / C ₀ (1)
The solvent contained in the electrophotographic liquid developer of the first invention is preferably substantially only the non-aqueous organic solvent (L), but preferably in the electrophotographic liquid developer. Other organic solvents may be contained in the range of 1% by weight or less, more preferably 0.5% by weight or less.

The core / shell type resin particles (C) constituting the electrophotographic liquid developer of the first invention may be resin particles produced by any method and process. Examples of the manufacturing method include the following manufacturing methods (1) to (3).
(1): A method of producing a core particle and simultaneously forming a core-shell structure.
Of the non-aqueous resin dispersion (W) of the resin particles (A) containing the first resin (a) and the organic solvent (M) of the second resin (b) [including its precursor (b0)] Method of forming resin particles (B) containing (b) in (W) by mixing solvent solution (O1) or (O2), dispersing (O1) or (O2) in (W) . In this case, simultaneously with the granulation of the resin particles (B), the resin particles (A) adhere to the surface of (B) to form the non-aqueous resin dispersion (X1) of the core-shell type resin particles (D). (B) It is made by removing the organic solvent (M) in which [including the precursor (b0)] is dissolved. At this time, if the surface of the resin particles is not formed into a film, a film-forming treatment is performed. This step may be performed at any stage as long as (X1) is obtained.

(2): The resin particles (B) containing the second resin (b) prepared in advance are coated with the coating agent (W ′) containing the first resin (a), and the shell layer is formed into a film. To produce core-shell type resin particles (C).
In this case, the coating agent (W ′) may be liquid, solid, or any form, and after coating with the precursor (a ′) of (a), (a ′) is reacted (a ). Further, (B) to be used may be resin particles produced by an emulsion polymerization aggregation method or the like, or resin particles produced by a pulverization method, or may be produced by any production method. The coating method is not limited. For example, the resin particles (B) or (B) prepared in advance in the non-aqueous resin dispersion (W) of the resin particles (A) containing the resin (a) are used. Examples thereof include a method of dispersing the resin dispersion and a method of sprinkling the solution (a) as a coating agent in (B).

(3): A method of producing core particles and changing the vicinity of the surface of the core particles to another shell resin by physically and / or chemically operating the core particles.
Resin particles (B) containing resin (b) are prepared in advance, and the surface of (B) is subjected to heat treatment and / or chemical treatment (such as acid and amine neutralization) to form single particles (B) as cores. There is a method of changing to shell type resin particles (C).
Among the methods (1) to (3), the method (1) is preferable.

The electrophotographic liquid developer according to the first invention is preferably obtained by the production method according to the second invention described below because resin particles having a uniform particle diameter are obtained.
In the production method of the second invention, the non-aqueous resin dispersion (W) of the resin particles (A) and the solvent solution (O1) of the organic solvent (M) of the resin (b) or the precursor of the resin (b) A solvent solution (O2) of the organic solvent (M) in (b0) is mixed, and (O1) or (O2) is dispersed in (W) to form resin particles (B) containing (b). The resin particles (A) are adsorbed on the surface of the resin particles (B) to prevent the resin particles (D) from uniting with each other, and (D) is split under high shear conditions. Make it harder. Thereby, the particle diameter of the resin particle (D) and the resin particle (C) obtained therefrom is converged to a constant value, and the effect of increasing the uniformity of the particle diameter is exhibited. Therefore, the resin particles (A) have such strength that they are not destroyed by shearing at the temperature at which they are dispersed, are not easily dissolved or swelled in the non-aqueous organic solvent (L) as a dispersion medium, A preferable characteristic is that it is difficult to dissolve in (O1) or (O2).

In the production method of the second invention, the resin particles (A) containing the first resin (a) are dispersed in the non-aqueous organic solvent (L) in the presence of the block copolymer (Z). A non-aqueous resin dispersion (W) and a solvent solution (O1) in which the second resin (b) is dissolved in an organic solvent (M) are mixed, and (O1) is dispersed in (W). In the non-aqueous resin dispersion (W) of (A), the resin particles (A) are adhered to the surfaces of the resin particles (B) by forming the resin particles (B) containing (b). A non-aqueous resin dispersion (X1) of resin particles (D) is obtained.
Or, in the non-aqueous organic solvent (L), in the presence of the block copolymer (Z), the non-aqueous resin dispersion (W) in which the resin particles (A) containing the resin (a) are dispersed; A solvent solution (O2) in which the precursor (b0) of the resin (b) is dissolved in the organic solvent (M), (O2) is dispersed in (W), and (b0) is further reacted. A structure in which the resin particles (A) are attached to the surfaces of the resin particles (B) by forming the resin particles (B) containing (b) in the non-aqueous resin dispersion (W) of (A). A non-aqueous resin dispersion (X1) of resin particles (D) is obtained.
Note that (b) and (b0) may be used in combination as a mixed solution.

The method of making the resin (a) into the non-aqueous resin dispersion (W) in which the resin particles (A) are dispersed in the non-aqueous organic solvent (L) is not particularly limited, but the following (1) to (6) ).
(1) In the case of vinyl resin, a non-aqueous resin dispersion of resin particles (A) is directly produced by a polymerization reaction such as a dispersion polymerization method in a solvent containing a non-aqueous organic solvent (L) using a monomer as a starting material. The solvent other than (L) is distilled off if necessary [When the solvent other than (L) is distilled off, a part of (L) (low boiling point component) may be distilled off. The same applies to the following solvent distillation step. ]Method.
(2) In the case of a polyaddition or condensation resin such as a polyester resin or a polyurethane resin, a non-aqueous organic solvent (L) in the presence of an appropriate dispersant, if necessary, a precursor (monomer, oligomer, etc.) or a solvent solution thereof. ), And after that, the precursor is cured by heating or adding a curing agent, and if necessary, the solvent other than (L) is distilled off to obtain a non-aqueous resin dispersion of resin particles (A). How to manufacture.
(3) In the case of a polyaddition or condensation resin such as a polyester resin or a polyurethane resin, in a precursor (monomer and oligomer, etc.) or a solvent solution thereof (preferably a liquid, which may be liquefied by heating) After dissolving an appropriate emulsifier, the non-aqueous organic solvent (L), which is a poor solvent, is added for reprecipitation, and the precursor is cured by adding a curing agent, and if necessary, a solvent other than (L) is retained. A method for producing a non-aqueous resin dispersion of resin particles (A).
(4) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc. The same shall apply hereinafter.) A method in which resin particles are obtained by pulverization using a fine pulverizer and the like and then dispersed in the non-aqueous organic solvent (L) in the presence of a suitable dispersant.
(5) After obtaining resin particles by spraying a resin solution (which may be polymerized in a solvent) in which a resin prepared in advance by a polymerization reaction is dissolved in a solvent, the resin particles are treated with an appropriate dispersant. A method of dispersing in a non-aqueous organic solvent (L) in the presence.
(6) a poor solvent [preferably a non-aqueous organic solvent (L)] is added to a resin solution (which may be polymerized in a solvent) in which a resin previously prepared by a polymerization reaction is dissolved in a solvent, or A method of precipitating resin particles in the presence of a suitable dispersant by cooling a resin solution heated and dissolved in advance in a solvent, and distilling off a solvent other than (L) if necessary.

Among these methods, the methods [1] and [6] are preferable, and the method [6] is more preferable.
Examples of the dispersant used in the methods [1] to [6] include the block copolymer (Z), the known surfactant (s), and the oil-soluble polymer (t). Of these, the block copolymer (Z) is preferred. Moreover, an organic solvent (u), a plasticizer (v), etc. can be used together as a dispersion aid.

  As the surfactant (s), an anionic surfactant (s-1), a cationic surfactant (s-2), an amphoteric surfactant (s-3) and a nonionic surfactant (s- 4) and the like. Two or more surfactants may be used in combination.

  As the anionic surfactant (s-1), an ether carboxylic acid (salt) having an alkyl group having 8 to 24 carbon atoms [(poly) oxyethylene (number of repeating units 1 to 100) sodium lauryl ether acetate or the like], Ether sulfate ester salt having an alkyl group having 8 to 24 carbon atoms [(poly) oxyethylene (repeating unit number 1 to 100) sodium lauryl sulfate, etc.], sulfosuccinate ester salt having an alkyl group having 8 to 24 carbon atoms [mono Or dialkyl sulfosuccinic acid ester di or mono sodium, (poly) oxyethylene (repeating unit number 1 to 100) mono or dialkyl sulfosuccinic acid ester di or mono sodium, etc.], (poly) oxyethylene (repeating unit number 1 to 100) coconut oil fatty acid Sodium monoethanolamide sulfate, carbon number 8 Sulfonate having 24 alkyl groups (such as sodium dodecylbenzenesulfonate), phosphate ester salt having an alkyl group having 8 to 24 carbon atoms [sodium lauryl phosphate and (poly) oxyethylene (number of repeating units 1 to 100) ) Sodium lauryl ether phosphate, etc.], fatty acid salts (such as sodium laurate and triethanolamine laurate), acylated amino acid salts (sodium coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid sodium, lauroylmethyl-β-alanine sodium, etc.).

  Examples of the cationic surfactant (s-2) include quaternary ammonium salt type and amine salt type cationic surfactants. Quaternary ammonium salt type cationic surfactants include tertiary amines and quaternizing agents (alkyl halides such as methyl chloride, methyl bromide, ethyl chloride and benzyl chloride, dimethyl sulfate, dimethyl carbonate, ethylene oxide, etc. For example, lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), cetylpyridinium chloride , Polyoxyethylene trimethyl ammonium chloride, stearamide ethyl diethyl methyl ammonium methosulfate, etc. And the like. As the amine salt type cationic surfactant, primary to tertiary amines are inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipine) Compounds obtained by neutralization with acid and alkyl phosphoric acid can be used, and primary amine salt type compounds such as higher aliphatic amines (laurylamine, stearylamine, cetylamine, hardened tallow amine, rosinamine, etc.) Higher amine) and higher fatty acid (stearic acid and oleic acid) salts of lower amines. Examples of the secondary amine salt type include inorganic acid salts or organic acid salts such as ethylene oxide adducts of aliphatic amines.

  Examples of the amphoteric surfactant (s-3) include carboxybetaine-type amphoteric surfactants [fatty acid amidopropyldimethylaminoacetic acid betaines having 10 to 18 carbon atoms (such as coconut oil fatty acid amidopropyl betaine), alkyls (having 10 to 18 carbon atoms). ) Dimethylaminoacetic acid betaine (such as lauryldimethylaminoacetic acid betaine), imidazolinium type carboxybetaine (such as 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine)], sulfobetaine type amphoteric surfactant [ C10-18 fatty acid amidopropylhydroxyethylsulfobetaine (coconut oil fatty acid amidopropyldimethylhydroxyethylsulfobetaine etc.), dimethylalkyl (C10-18) dimethylhydroxyethylsulfobetaine (laurylhydroxys) Hobetain etc.), amino acid type amphoteric surfactants (beta-lauryl amino sodium propionate and the like).

Examples of the nonionic surfactant (s-4) include alkylene oxide addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants.
Examples of the alkylene oxide addition type nonionic surfactant include higher alcohols (8 to 18 carbon atoms) alkylene (2 to 4 carbon atoms, preferably 2) oxide adducts (1 to 1 moles added per active hydrogen). 30), alkyl (carbon number 1-12) phenol ethylene oxide adduct (addition mole number 1-30), higher amine (carbon number 8-22) alkylene (carbon number 2-4, preferably 2) oxide adduct (Addition mole number per active hydrogen 1-40), fatty acid (carbon number 8-18) ethylene oxide adduct (addition mole number 1-60 per active hydrogen), polypropylene glycol (Mn = 200-4) , 000) ethylene oxide adduct (addition mole number per active hydrogen 1-50), polyoxyethylene (repeat unit number 3-30) alkyl (C6-C20) allyl ether and sorbitan monolaurate ethylene oxide adduct (addition moles 1-30 per active hydrogen) and sorbitan monooleate ethylene oxide adduct (addition moles per active hydrogen) Fatty acid (carbon number 8-24) ester ethylene oxide adduct of polyhydric (2-8 valence or higher) alcohol (carbon number 2-30) such as 1-30) 30).
Examples of the polyhydric alcohol type nonionic surfactant include polyvalent (2 to 8 or more) alcohols (2 to 30 carbon atoms) such as glycerin monostearate, glycerin monooleate, sorbitan monolaurate and sorbitan monooleate. ) Fatty acid (carbon number 8-24) ester and fatty acid (carbon number 10-18) alkanolamide such as lauric acid monoethanolamide and lauric acid diethanolamide.

Examples of the oil-soluble polymer (t) include a polymer having at least one group of an alkyl group having 4 or more carbon atoms, a dimethylsiloxane group, or a functional group having a fluorine atom. Furthermore, it preferably has a chemical structure having an affinity for the resin (b) while having a functional group having an alkyl group, a dimethylsiloxane group or a fluorine atom having an affinity for the non-aqueous organic solvent (L).
Specifically, among the vinyl monomers, a monomer having an alkyl group having 4 or more carbon atoms, a monomer having a dimethylsiloxane group (or a reactive oligomer), and / or a monomer having a fluorine atom, and the above-described resin ( A copolymer with a vinyl monomer constituting b) is preferred. The form of copolymerization may be random, block or graft, but block or graft is preferred.

  The organic solvent (u) used to obtain the non-aqueous resin dispersion (W) of the resin particles (A) is an organic solvent other than the non-aqueous organic solvents (L) and (L). Examples of the organic solvent (M) described later which do not correspond to (L)]. Since the solvent other than (L) needs to be distilled off when preparing the non-aqueous resin dispersion (W), the boiling point is lower than that of (L) used in the dispersion medium of (W), and the solvent is not distilled off. What is easy is preferable.

Even if the plasticizer (v) is added to the non-aqueous organic solvent (L) as necessary during dispersion, the plasticizer (v) in the dispersion [the solvent of the organic solvent (M) containing the resin (b) or (b0)] In solution (O1) or (O2)].
There is no limitation in particular as a plasticizer (v), The following are mentioned.
(V1) Phthalates (dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, etc.);
(V2) aliphatic dibasic acid esters (di-2-ethylhexyl adipate and 2-ethylhexyl sebacate, etc.);
(V3) trimellitic acid ester (trimellitic acid tri-2-ethylhexyl, trimellitic acid trioctyl, etc.);
(V4) Phosphate ester (triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.);
(V5) fatty acid esters (such as butyl oleate);
(V6) and a mixture of two or more of these.

  The particle size of the resin particles (A) in the present invention is usually smaller than the particle size of the formed resin particles (B), and from the viewpoint of particle size uniformity, the particle size ratio [volume average of resin particles (A) The value of [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 larger than 0.3, (A) is not efficiently adsorbed on the surface of (B), so that the particle size distribution of the obtained resin particles (D) and (C) tends to be wide.

The volume average particle size of the resin particles (A) can be appropriately adjusted within the above range of particle size ratios so as to be a particle size suitable for obtaining the resin particles (C) having a desired particle size.
The volume average particle diameter of (A) is 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 resin particles (C) having a volume average particle diameter of 1 μm, the range is preferably 0.0005 to 0.3 μm, more preferably 0.001 to 0.2 μm, and 10 μm resin particles ( When it is desired to obtain C), it is preferably 0.005 to 3 μm, more preferably 0.05 to 2 μm, and when it is desired to obtain 100 μm particles (C), preferably 0.05 to 30 μm, more preferably 0.1 to 20 μm.
The volume average particle size is determined by laser type particle size distribution measuring apparatus “LA-920” (manufactured by Horiba, Ltd.) or “Multisizer III” (manufactured by Coulter), and “ELS-800” using a laser Doppler method as an optical system. [Otsuka Electronics Co., Ltd.] can be measured. If there is a difference in the measured value of the particle diameter between the measuring devices, the measured value of “ELS-800” is adopted.
In addition, since the said particle size ratio is easy to obtain, the volume average particle diameter of the resin particle (B) described later is preferably 0.1 to 300 μm, more preferably 0.5 to 250 μm, particularly preferably 1 to 1. 200 μm.

The adsorption force of the resin particles (A) for obtaining the resin particles (D) and (C) to the resin particles (B) can be controlled by the following method.
[1] When the non-aqueous resin dispersion (X1) is produced, if the resin particles (A) and the resin particles (B) are made to have positive and negative charges, an adsorption force is generated. The greater the charge of each of A) and resin particles (B), the stronger the adsorptive power and the greater the coverage of the resin particles (A) on the resin particles (B).
[2] When the non-aqueous resin dispersion (X1) is produced, if the resin particles (A) and the resin particles (B) are charged with the same polarity (both positive or negative), the coverage rate Tend to go down. In this case, in general, when the surfactant (s) and / or the oily polymer (t) [particularly those having a reverse charge to the resin particles (A) and the resin particles (B)] are used, the adsorptive power becomes strong and the coverage rate is increased. Goes up.
[3] When the SP value difference between the resin (a) and the resin (b) is reduced, the adsorption force is increased and the coverage is increased.

  When dispersing the solvent solution (O1) of the resin (b) or the solvent solution (O2) of the precursor (b0) of the resin (b), a dispersing device can be used. The dispersion apparatus is not particularly limited as long as it is generally marketed as an emulsifier and a disperser. For example, a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer [specialized machinery industry ( Co., Ltd.] batch type emulsifiers, Ebara Milder [manufactured by Ebara Corporation], TK Philmix, TK Pipeline Homo Mixer [manufactured by Special Machine Industries Co., Ltd.], colloid mill [Shinko Pantech ( Co., Ltd.], Slasher, Trigonal wet milling machine [Mitsui Miike Chemical Co., Ltd.], Captron (Eurotech Co., Ltd.), Fine Flow Mill [Pacific Kiko Co., Ltd.], etc. High-pressure emulsifiers such as Fluidizer [manufactured by Mizuho Kogyo Co., Ltd.], Nanomizer (manufactured by Nanomizer), APV Gaurin (manufactured by Gaurin), membrane emulsifier [cooling industry Ltd.] and the like of the film emulsifying machine, Vibro Mixer [Hiyaka Kogyo Co., Ltd.] 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 uniform particle size.

The viscosity of the solvent solution (O1) of the resin (b) or the solvent solution (O2) of the precursor (b0) is preferably 10 to 50,000 mPa · s (measured with a B-type viscometer from the viewpoint of particle size uniformity. And more preferably 100 to 10,000 mPa · s.
The temperature at the time of dispersion is preferably 0 to 150 ° C. (under pressure), more preferably 5 to 98 ° C. When the viscosity of the non-aqueous resin dispersion (X1) is high, it is preferable to carry out dispersion by raising the temperature and lowering the viscosity to the above preferred range.
The organic solvent (M) used for the solvent solution of the resin (b) or the precursor (b0) may be any solvent that can dissolve the resin (b) at room temperature or under heating, but the SP value is preferably 8. 5~20 (cal ^/ cm ^{3) 1/2,} still more preferably ^{10~19 (cal / cm 3) 1/2} . When using a mixed solvent as (M), the SP value is assumed to be additive, and the weighted average value calculated from the SP value of each solvent may be within the above range. If the SP value is outside the above range, the solubility of (b) or (b0) may be insufficient.

As the organic solvent (M), those suitable for the combination with the resin (b) or the precursor (b0) of the resin (b) within the range of the above SP value can be appropriately selected. Toluene, xylene, ethylbenzene And aromatic hydrocarbon solvents such as tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit and cyclohexane; methyl chloride, methyl bromide, methyl iodide, methylene dichloride, Halogen solvents such as carbon tetrachloride, trichlorethylene and perchloroethylene; ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate and ethyl cellosolve acetate; diethyl ether, THF, dioxane, ethyl Cellosolve, butylcellosolve and Ether solvents such as propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t- Alcohol solvents such as butanol, 2-ethylhexyl alcohol and benzyl alcohol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methylpyrrolidone; The mixed solvent of seed | species or more is mentioned.
The boiling point of (M) is preferably 100 ° C. or less, and more preferably 90 ° C. or less, from the viewpoint of odor and being easily distilled off from the non-aqueous resin dispersion (X1).

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

  The 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. The resin (b) is a condensation resin (for example, polyurethane resin, epoxy resin, and polyester resin). Etc.), when (b0) is a combination of the prepolymer (α) having a reactive group and the curing agent (β), and the resin (b) is a vinyl resin, (b0) Vinyl monomers (which may be used alone or in combination of two or more) and solvent solutions thereof.

  When a vinyl monomer is used as the precursor (b0), the method of reacting the precursor (b0) to obtain the resin (b) includes, for example, an oil-soluble initiator, monomers, and an organic solvent (M). A method in which an oil phase is dispersed and suspended in a non-aqueous organic solvent (L) in the presence of an oil-soluble polymer (t) and a radical polymerization reaction is performed by heating (so-called suspension polymerization method), monomers and an organic solvent (M ) Is emulsified in a non-aqueous resin dispersion (W) of resin particles (A) containing a dispersant [same as the surfactant (s)], an oil-soluble initiator, Examples thereof include a method of performing a radical polymerization reaction by heating (so-called dispersion polymerization method).

  Examples of the oil-soluble initiator include peroxide polymerization initiator (I) and azo 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) Oil-soluble peroxide polymerization initiator:
Acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, 2,4-dichlorobenzoyl peroxide, t-butyl peroxybivalate, octanoyl peroxide, lauroyl Peroxide, propionitrile peroxide, succinic acid peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, parachlorobenzoyl peroxide, t-butylperoxyisobutyrate , T-butylperoxymaleic acid, t-butylperoxylaurate, cyclohexanone peroxide, t-butylperoxyisopropyl -Bonate, t-butylperoxyacetate, t-butylperoxybenzoate, diisobutyldiperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, t-butylcumyl peroxide, t-butylhydroperoxide, di-t-butylperoxide Oxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene peroxide and the like.

(II) 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) and 2,2'-azobis ( 4-methoxy-2,4-dimethylvaleronitrile) and the like.

(III) Non-aqueous redox polymerization initiator:
Oil-soluble peroxides such as hydroperoxides, dialkyl peroxides and diacyl peroxides, and oil-soluble reductions such as tertiary amines, naphthenates, mercaptans, organometallic compounds (such as triethylaluminum, triethylboron and diethylzinc) Combined with an agent.

  As the precursor (b0), a combination of a prepolymer (α) having a reactive group and a curing agent (β) can also be used. Here, the “reactive group” refers to a group that can react with the curing agent (β). In this case, as a method of forming the resin (b) by reacting the precursor (b0), a solvent solution containing a reactive group-containing prepolymer (α), a curing agent (β), and an organic solvent (M), Resin particles containing resin (b) by dispersing the resin particles (A) in the non-aqueous resin dispersion (W) and reacting the reactive group-containing prepolymer (α) with the curing agent (β) by heating ( Method for forming B): A solvent solution of the reactive group-containing prepolymer (α) is dispersed in the non-aqueous resin dispersion (W) of the resin particles (A), and an oil-soluble curing agent (β) is added thereto. In addition, a method of reacting to form resin particles (B) containing the resin (b);

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). The combination.
[2] A combination in which the reactive group of the reactive group-containing prepolymer (α) is an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) that can react with the active hydrogen-containing group. .
Of these, [1] is preferable from the viewpoint of reaction rate.
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 An acid halide group (α1e) and the like can be mentioned. Of these, (α1a), (α1b) and (α1c) are preferred, and (α1a) and (α1b) are more preferred.
Here, the blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent.
Examples of the blocking agent include oximes (acetoxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.); lactams (γ-butyrolactam, ε-caprolactam, and γ-valerolactam) C1-20 aliphatic alcohols (ethanol, methanol, octanol, etc.); phenols (phenol, m-cresol, xylenol, nonylphenol, etc.); active methylene compounds (acetylacetone, ethyl malonate, and ethyl acetoacetate) Etc.); basic nitrogen-containing compounds (N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.); and mixtures of two or more thereof And the like.
Of these, oximes are preferred, and methyl ethyl ketoxime is more 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 more preferred.
Examples of the polyether (αw) include polyethylene oxide, polypropylene oxide, polybutylene oxide, and polytetramethylene oxide.
Examples of polyester (αx) include polycondensates of diol (11) and dicarboxylic acid (13), polylactones (ε-caprolactone ring-opening polymer), and the like.
Examples of the epoxy resin (αy) include addition condensates of bisphenols (such as bisphenol A, bisphenol F and bisphenol S) and epichlorohydrin.
Examples of polyurethane (αz) include a polyaddition product of diol (11) and polyisocyanate (15) and a polyaddition product of polyester (αx) and polyisocyanate (15).

As a method of incorporating reactive groups into polyester (αx), epoxy resin (αy), polyurethane (αz), etc.,
[1] A method of leaving a functional group of a constituent component at the terminal by excessively using one of two or more constituent components,
[2] A compound containing a functional group capable of reacting with the remaining functional group and a reactive group by leaving one of the two or more structural components in excess to leave the functional group of the structural component at the terminal. How to react,
Etc.
In the 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, and an isocyanate A group-containing polyurethane prepolymer or the like is obtained.
For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is such that the ratio of the polyol (1) to the polycarboxylic acid (2) is the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [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 method [2], an isocyanate group-containing prepolymer is obtained by reacting the preprimer obtained in the method [1] with a polyisocyanate, and a blocked polyisocyanate is reacted with the 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 such that, for example, when a polyisocyanate is reacted with a hydroxyl group-containing polyester to obtain an isocyanate group-containing polyester prepolymer, the ratio of the polyisocyanate is an isocyanate group [NCO] and a hydroxyl group. The equivalent ratio [NCO] / [OH] of the hydroxyl group [OH] of the contained polyester is preferably 5/1 to 1.01 / 1, more preferably 4/1 to 1.2 / 1, particularly preferably 2. .5 / 1 to 1.5 / 1. In the case of prepolymers having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is preferably 1 or more, more preferably 1.5 to 3 on average, and particularly preferably 1.8 to 2 on average. .5. By setting it as the said range, Mn and Mw of the hardened | cured material obtained by making it react with a hardening | curing agent ((beta)) become high.
The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000.
The Mw of the reactive group-containing prepolymer (α) is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and particularly preferably 4,000 to 20,000.
The viscosity of the reactive group-containing prepolymer (α) is preferably 2,000 poise or less at 100 ° C., more preferably 1,000 poise or less. By setting it to 2,000 poise or less, it is preferable in that the resin particles (D) and (C) having a sharp particle size distribution can be obtained.

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

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

Examples of the polyol (β1b) include those similar to the diol (11) and the trivalent to octavalent or higher polyol (12). Preferred among (β1b) are diol (11) alone and a mixture of diol (11) and a small amount of polyol (12).
Examples of the polymercaptan (β1c) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

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

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 these 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 more preferred.
Examples of the organic group blocked with a compound from which an amino group can be eliminated include the same groups as those described above for (β1a).

  Examples of the compound (β2) capable of reacting with the active hydrogen-containing group include polyisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polycarboxylic acid anhydride (β2d), and polyacid halide (β2e). Can be mentioned. Of these, (β2a) and (β2b) are preferred, and (β2a) is more preferred.

Examples of the polyisocyanate (β2a) include the same as the polyisocyanate (15), and preferred ones are also the same.
Examples of the polyepoxide (β2b) include the same as 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). Preferred are (β2c-1) alone and (β2c-1) It is a mixture of a small amount of (β2c-2).
The dicarboxylic acid (β2c-1) is the same as the dicarboxylic acid (13), and the polycarboxylic acid (β2c-2) is the same as the tricarboxylic acid or trivalent or higher polycarboxylic acid (14). 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 acid halides (acid chloride, acid bromide, acid iodide, etc.) of the above (β2c).
Furthermore, if necessary, a reaction terminator (βs) can be used in combination with (β2).

  The ratio of the curing agent (β) is the ratio of the equivalent [α] of the reactive group in the reactive group-containing prepolymer (α) to the equivalent of the active hydrogen-containing group [β] in the curing agent (β) [α. ] / [Β] is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and particularly preferably 1.2 / 1 to 1 / 1.2. . In addition, when a hardening | curing agent ((beta)) is water, water is handled as a bivalent active hydrogen compound.

  Resin (b) obtained by reacting a precursor (b0) composed of a reactive group-containing prepolymer (α) and a curing agent (β) in a non-aqueous medium comprises resin particles (B) and resin particles (C). It becomes a component of. 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. Is 5,000 to 1,000,000.

  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) in a non-aqueous medium (so-called dead polymer). Can also be contained in the system. In this case, the resin (b) is a mixture of a resin obtained by reacting a reactive group-containing prepolymer (α) and a curing agent (β) in a non-aqueous medium, and a resin not reacted (dead polymer). Become.

  The amount of the non-aqueous resin 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. is there. If it is 50 parts by weight or more, the dispersion state of the resin (b) is good, and if it is 2,000 parts by weight or less, it is economical.

In the production method of the second invention, the organic solvent (M) is removed from the non-aqueous resin dispersion (X1) of the resin particles (D) having a structure in which the resin particles (A) are adhered to the surfaces of the resin particles (B). On the condition that the non-aqueous organic solvent (L) remains in the dispersion, it is preferably retained until it becomes 1% by weight or less (more preferably 0.5% by weight or less) in the obtained non-aqueous resin dispersion (X2). Leave. However, a part (low boiling point component) of (L) may be distilled off together with (M).
As a method of distilling off, a method of distilling off at a temperature not lower than 20 ° C. and not higher than the boiling point of (M) under a reduced pressure of 20 to 500 mmHg can be mentioned.

In the production method of the second invention, by using the resin (a) having a molecular chain (k) having a high affinity for the organic solvent (L) in the side chain, particularly when using the following preferred solvents, The solvent (M) is preferably used in the non-aqueous resin dispersion (X1) in an amount of 10 to 50% by weight (more preferably 20 to 40% by weight), and 40 ° C. or less, preferably 1% by weight or less (more preferably 0.8%). The resin particles (A) are dissolved in the solvent to form a film by removing the solvent (M) until 5 wt% or less), and the resin (a) is formed on the surface of the core layer (Q) composed of (B). In many cases, a non-aqueous resin dispersion (X2) of resin particles (C) in which a film-like shell layer (P) containing) is formed is obtained.
From the viewpoint of film formation, (M) is preferably tetrahydrofuran, toluene, acetone, methyl ethyl ketone and ethyl acetate, and more preferably acetone and ethyl acetate.

When the film of (A) is not formed on the surface of the core layer (Q) composed of (B), or when the film is formed of (A) on a part of the surface of the core layer (Q) However, in order to further improve the smoothness of the coating on the surface of the resin particles (C), when the following operation is performed, at least a part of the surface of the core layer (Q) composed of (B), preferably the entire surface In addition, a non-aqueous resin dispersion (X2) of resin particles (C) having a smooth coating-like shell layer (P) formed by (A) is obtained, and the resin particles (C) in (X2) From the viewpoint of excellent dispersion stability.
Examples of the method include a method of dissolving (A) attached to (B) in a solvent and a method of heating the nonaqueous resin dispersion (X1) to melt (A) to form a film. These methods may be used in combination.

The solvent used when the resin particles (A) are dissolved to form a film may be added to (X1) when forming the film, but the resin (b) is used as a raw material for obtaining (X1). Alternatively, the organic solvent (M) used in the solvent solution of the precursor (b0) is not removed immediately after the formation of the resin particles (B), but is used because the solvent is contained in (B) ( The dissolution of A) is easy, and it is preferable that the resin does not aggregate.
The concentration of the organic solvent (M) in the non-aqueous resin dispersion (X1) when (A) is dissolved in the solvent is preferably 3 to 50% by weight, more preferably 10 to 40% by weight, particularly Preferably it is 15-30 weight%. Moreover, melt | dissolution is performed by stirring nonaqueous resin dispersion liquid (X1) for 1 to 10 hours, for example, The temperature at the time of melt | dissolution becomes like this. Preferably it is 15-45 degreeC, More preferably, it is 15-30 degreeC. .

When (A) is melted to form a film on the surface of the core layer (Q) composed of (B), the solid content in the non-aqueous resin dispersion (X1) [content of components other than the solvent] Is preferably 1 to 50% by weight, more preferably 5 to 30% by weight. The content of the organic solvent (M) at this time is preferably 2% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.5% by weight or less. When the solid content in (X1) is high or the content of the organic solvent (M) exceeds 2% by weight, aggregates may be generated when (X1) is 60 ° C. or higher. The heating conditions at the time of melting are not particularly limited as long as (A) is melted. For example, it is preferably 40 to 100 ° C., more preferably 60 to 90 ° C., and particularly preferably 60 to 80 under stirring. A method of heating at a temperature of preferably 1 to 300 minutes can be mentioned.
In addition, as a method of film-forming treatment, the non-aqueous resin dispersion (X1) of the resin particles (D) having an organic solvent (M) content of 2% by weight or less is heat-treated, A preferable heat treatment temperature when melting on the core layer (Q) is not less than Tg of the resin (a) and preferably in a temperature range of not more than 80 ° C. The surface smoothness of the resin particles (C) obtained when the heat treatment temperature is lower than the Tg of (a) hardly changes. Moreover, when heat-processing at the temperature exceeding 80 degreeC, a shell layer (P) may peel from a core layer (Q).
Of these (A) film forming methods, the method of melting (A) and the method of dissolving (A) and the method of melting (A) are preferred.

The control of the shape of the resin particles (C) constituting the non-aqueous resin dispersion (X2) obtained by the production method of the second invention is controlled by the difference in SP value between the resin (a) and the resin (b), or the resin (a The particle shape and particle surface property can be controlled by controlling Mw. When the SP value difference is small, it is easy to obtain irregular and smooth surface particles, and when the SP value difference is large, it is easy to obtain spherical and rough particles. Moreover, when the Mw of (a) is large, particles having a rough surface are easily obtained, and when the Mw is small, particles having a smooth surface are easily obtained. However, if the difference in SP value between (a) and (b) is too small or too large, granulation becomes difficult. If the Mw 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 particularly preferably 0.2 to 2.0. . The Mw of the resin (a) is preferably from 1,000 to 1,000,000, more preferably from 1,000 to 500,000, particularly preferably from 2,000 to 200,000, and most preferably from 3,000 to 100,000.

  In the production method of the second invention, from the viewpoint of the particle size uniformity of the resin particles (C), the storage stability of the non-aqueous resin dispersion (X2), etc., the resin particles (C) are 1 It is composed of a film-like shell layer (P) containing ˜70 wt% resin (a) and a core layer (Q) containing 30 ˜99 wt% resin (b). Preferably, it is composed of 5 to 50 wt% (P) and 50 to 95 wt% (Q), more preferably 10 to 35 wt% (P) and 65 to 90 wt% (Q). is there.

From the viewpoints of particle size uniformity of the resin particles (C), fluidity of the non-aqueous resin dispersion (X2), storage stability, etc., the resin particles (C) preferably have 5 wt% of the surface of the resin particles (B). % Or more, more preferably 30% by weight or more, particularly preferably 50% by weight or more, and most preferably 80% by weight or more is covered with the coating (P) of the resin (a). The surface coverage of (C) can be determined based on the following equation from image analysis of an image obtained with a scanning electron microscope (SEM).
Surface coverage (%) = [area of the portion covered by the shell layer (P) / area of the portion covered by the shell layer (P) + area of the portion where the core layer (Q) is exposed] × 100

The coefficient of variation in volume distribution of the resin particles (C) is preferably 30% by weight or less, more preferably 1 to 26% by weight, from the viewpoint of particle size uniformity.
The coefficient of variation of the volume distribution is measured by a particle size distribution measuring device such as a laser particle size distribution measuring device “LA-920” [manufactured by Horiba, Ltd.].
The value of [volume average particle size / number average particle size] of the resin particles (C) is preferably 1.0 to 1.4, more preferably 1.0 to 1.1, from the viewpoint of particle size uniformity. 2.
The volume average particle diameter of (C) is preferably 0.1 to 300 μm. The upper limit is more preferably 250 μm, particularly preferably 200 μm, and most preferably 100 μm. The lower limit is more preferably 0.5 μm, and 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 (C) constituting the electrophotographic liquid developer of the present invention are based on the particle size of the resin particles (A) and the resin particles (B) and the film-like shell layer (P) containing the resin (a). By changing the coverage of the resin particle (B) surface, it is possible to make the particle surface have desired irregularities. The surface average center line roughness (Ra) of (C) is preferably 0.01 to 0.8 μm from the viewpoint of fluidity. (Ra) is a value obtained by arithmetically averaging the absolute value of the deviation between the roughness curve and its center line, and can be measured by, for example, a scanning probe microscope system [manufactured by Toyo Technica Co., Ltd.].

  The shape of the resin particles (C) is preferably spherical from the viewpoints of fluidity and melt leveling. In that case, the resin particles (B) are preferably spherical. The average circularity of (C) is preferably 0.96 to 1.0, more preferably 0.97 to 1.0, and particularly preferably 0.98 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]. Specifically, 100 to 150 ml of water from which impure solids have been removed in advance is placed in a predetermined container, and a surfactant “Dry Well” [manufactured by Fuji Photo Film Co., Ltd.] 0.1 to 0.5 ml is added as a dispersant. In addition, about 0.1 to 9.5 g of the measurement sample is further added, and the suspension in which the sample is dispersed is dispersed for about 1 to 3 minutes with an ultrasonic disperser “Ultrasonic Cleaner Model VS-150” (manufactured by Wellboclear). The dispersion concentration is set to 3,000 to 10,000 particles / μL, and the shape and distribution of the resin particles are measured.

The resin particles (C) constituting the non-aqueous resin dispersion (X2) obtained by the production method of the second invention are resin particles (B) produced by the resin particles (A) when the non-aqueous resin dispersion (X1) is produced. ) By changing the surface coverage and the depth at which the resin particles (A) are embedded on the resin particle (B) side on the non-aqueous medium interface, the particle surface is smoothed or desired irregularities are given to the particle surface. You can do it.
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 producing a non-aqueous resin dispersion (X1) of resin particles (D), the resin particles (A) and the resin particles (B) are made to have positive and negative charges. The coverage of the surface of the resin particles (B) is increased, and the depth at which the resin particles (A) are embedded on the resin particle (B) side is increased. In this case, as the charges of the resin particles (A) and the resin particles (B) are increased, the coverage is further increased and the depth is increased.
[2] When producing the non-aqueous resin dispersion (X1) of the resin particles (D), the resin particles (A) and the resin particles (B) have the same polarity (both positive or negative). If it does so, there exists a tendency for a coverage to fall and for the depth to become small. In this case, generally, when the surfactant (s) and / or the oil-soluble polymer (t) [preferably those having a reverse charge to the resin particles (A) and the resin particles (B)] are used, the coverage is increased. Further, when the oil-soluble polymer (t) is used, the depth decreases as the Mw of the oil-soluble polymer (t) increases.
[3] The coverage increases as the SP value difference between the resin (a) and the resin (b) decreases, and the depth increases.

Additives (pigments, fillers, antistatic agents, colorants, release agents, charge control agents, ultraviolet absorbers) in the shell layer (P) and / or the core layer (Q) constituting the resin particles (C) , Antioxidants, anti-blocking agents, heat stabilizers, flame retardants, etc.). As a method of adding an additive into the shell layer (P) or the core layer (Q), the additive may be mixed when forming the non-aqueous resin dispersion (X1) of the resin particles (D). More preferably, after mixing (a) or resin (b) and an additive, the mixture is added and dispersed in a non-aqueous medium.
In the present invention, the additive does not necessarily have to be mixed when the particles are formed in (X1), and may be added after the particles are formed. For example, after forming particles not containing a colorant, a colorant is added by a known dyeing method, or the additive is impregnated with the organic solvent (u) and / or the plasticizer (v). You can also.

As the additive, it is preferable that the core layer (Q) contains the wax (c) and / or the modified wax (d) grafted with a vinyl polymer chain together with the resin (b) because the heat-resistant storage stability is further improved.
The content of (c) in (Q) is preferably 20% by weight or less, more preferably 1 to 15% by weight. The content of (d) in (Q) is preferably 10% by weight or less, more preferably 0.5 to 8% by weight. The total content of (c) and (d) in (Q) is preferably 25% by weight or less, more preferably 1 to 20% by weight.

Examples of the wax (c) include synthetic wax (polyolefin wax) and natural wax (paraffin wax, microcrystalline wax, carnauba wax, carbonyl group-containing wax, and a mixture thereof). Of these, paraffin wax (c1) and carnauba wax (c2) are preferred. Examples of (c1) include petroleum-based waxes mainly composed of linear saturated hydrocarbons having a melting point of 50 to 90 ° C. and 20 to 36 carbon atoms, and (c2) includes a melting point of 50 to 90 ° C. and 16 carbon atoms. -36 animal and plant waxes.
Mn in (c) is preferably 400 to 5,000, more preferably 1,000 to 3,000, and particularly preferably 1,500 to 2,000 from the viewpoint of releasability. In the above and below, Mn of wax (c) is measured using GPC (solvent: orthodichlorobenzene, reference material: polystyrene).

  The wax (c) is melt-kneaded in the absence of a solvent and / or heated and dissolved and mixed in the presence of the organic solvent (u) together with the modified wax (d) grafted with a vinyl polymer chain, and then the resin (b) It is preferable to be dispersed. By the coexistence of the modified wax (d) during the wax dispersion treatment by this method, the wax base part of (d) is efficiently adsorbed on the surface or partly entangled in the matrix structure of the wax (c). Thus, 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 control of the dispersion state is facilitated.

  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 the same monomers as 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 unreacted wax) in the modified wax (d) is preferably 0.5 to 99.5% by weight, more preferably 1 to 80% by weight, particularly preferably 5 to 50% by weight. Most preferably, it is 10 to 30% by weight.
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 non-aqueous resin dispersion (X2).
The Mn in (d) is preferably 1,500 to 10,000, more preferably 1,800 to 9,000. If Mn is in the range of 1500 to 10,000, the mechanical strength of the resin particles (C) will be good.

The modified wax (d) is polymerized by, for example, dissolving or dispersing the wax (c) in a solvent (toluene, xylene, etc.) and heating to 100 to 200 ° C., and then dropping a vinyl monomer together with a peroxide polymerization initiator. It can be obtained by distilling off the solvent.
The amount of the peroxide polymerization initiator in the synthesis of the modified wax (d) is preferably 0.2 to 10% by weight, more preferably 0.5 to 5%, based on the total weight of the raw materials of (d). % By weight.

  Examples of the peroxide-based polymerization initiator include those similar to those exemplified as the oil-soluble peroxide-based polymerization initiator.

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 depositing in a liquid by cooling crystallization, solvent crystallization or the like, or depositing in a gas by spray drying or the like, [3] (c) and (d) are dissolved in an organic solvent (u And the like, and a method of mechanically wet pulverizing with a disperser. Of these, the method [2] is preferred.
As a method of dispersing the wax (c) and the modified wax (d) in (b), (c), (d), and (b) are respectively made into a solvent solution or a dispersion, and then mixed together. And the like.

In the electrophotographic liquid developer of the first invention, the particle size and shape of the resin particles in the dispersion are uniform. Therefore, the electrophotographic liquid developer of the present invention is also useful for paints, oil-based inks for inkjet printers, inks for electronic paper, cosmetics, spacers for manufacturing electronic components, and electrorheological fluids. When used in these applications, known dyes, pigments and magnetic powders can be added to the resin particles (C) as colorants. Specific examples of colorants include carbon black, Sudan Black SM, First Yellow-G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Priliant Green, Phthalocyanine Green, Oil Yellow GG, Kaya Set YG, Orazol Brown B, Oil Pink OP, Magnetite and Iron Black etc. Can be mentioned.
The use rate of the colorant is preferably 0.5 to 15% by weight based on the weight of the resin (b) when using a dye or pigment, and preferably 20 to 20 when using magnetic powder. 150% by weight.
In order to control the chargeability of the resin particles (C), as a charge control agent, for example, nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary Examples thereof include ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorosurfactants, salicylic acid metal salts and metal salts of salicylic acid derivatives. Specifically, the nigrosine dye “bontron 03”, the quaternary ammonium salt “bontron P-51”, the metal-containing azo dye “bontron S-34”, and the oxynaphthoic acid metal complex “E-82”. ”, Salicylic acid metal complex“ E-84 ”, phenolic condensate“ E-89 ”[manufactured by Orient Chemical Co., Ltd.], quaternary ammonium salt molybdenum complex“ TP-302 ”,“ "TP-415" [above, manufactured by Hodogaya Chemical Co., Ltd.], quaternary ammonium salt "copy charge PSY VP2038", triphenylmethane derivative "copy blue PR", quaternary ammonium salt "copy charge" NEG VP2036 "," Copy Charge NX VP434 "(manufactured by Hoechst)," LRA-901 ", boron complex" LR-147 " [Japan Carlit Co., Ltd.], copper phthalocyanine, perylene, quinacridone, azo pigments, a sulfonic acid group, polymer compounds or the like having a functional group such as a carboxyl group or a quaternary ammonium salt.
The usage rate of the charge control agent is preferably 0 to 5% by weight based on the weight of the resin (b).

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

<Production Example 1> [Production of block copolymer (Z) solution]
In a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel and nitrogen blowing tube, 250 parts of THF and 2.18 parts of methylketenemethyltrimethylsilylacetal as a polymerization initiator were charged, and the inside of the reaction system was purged with nitrogen. . 0.3 parts of a 1 mol / L acetonitrile solution of tetrabutylammonium-m-chlorobenzoate as a catalyst was added, and 100 parts of methyl methacrylate was added dropwise from a dropping funnel over 1 hour at 40 ° C. Next, 12.5 parts of dimethylaminoethyl methacrylate was added dropwise from a dropping funnel over 20 minutes to cause a polymerization reaction for 1 hour, and then 1 part of methanol was added to stop the reaction. The obtained block copolymer (Z ′) in THF solution was added to 500 parts of hexane to reprecipitate the block copolymer (Z ′), and purified by filtration and vacuum drying to obtain a block copolymer (Z ') Got.
In a reaction vessel equipped with a stirrer, 43 parts of propylene glycol monomethyl ether acetate and 10 parts of block copolymer (Z ′) are added and stirred at 25 ° C. for 1 hour to produce the block copolymer (Z ′) in propylene glycol. Dissolved in monomethyl ether acetate. Next, 0.77 part of ethylphosphonic acid that is a salt-forming component [1.0 mol% based on the amino group of the block copolymer (Z ′)] was added, and the mixture was stirred at 40 ° C. for 2 hours. A [block copolymer (Z) solution] having a solid concentration of 20% by weight was prepared. The block copolymer (Z) has a composition ratio of methyl methacrylate: dimethylaminoethyl methacrylate) = 8/1 (weight ratio), Mw = 9,800, Mn = 8,300, Mw / Mn = 1. .18.

<Production Example 2> [Production of non-aqueous resin dispersion (W) of resin particles (A)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a dropping funnel, and a nitrogen blowing tube, 200 parts of THF was charged, and in another glass beaker, 120 parts of methyl methacrylate, methacryl-modified silicone “X-22— 2426 "(manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.5 part of azobismethoxydimethylvaleronitrile were added and stirred at 20 ° C for 20 minutes to prepare a monomer solution, which was then added to a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 40 ° C. for 1 hour in a sealed state. Three hours after the completion of the dropwise addition, a mixture of 0.5 part of azobismethoxydimethylvaleronitrile and 20 parts of THF was added to the reaction vessel, aged at 40 ° C. for 3 hours, and then cooled to room temperature. 50 parts of this polymerization solution was further added dropwise to 80 parts of liquid paraffin [relative dielectric constant: 2.0, SP value: 8.6 (cal / cm ³ ) ^1/2 ] under stirring, and a reduced pressure of 40 ° C. and 300 mmHg. Under reduced pressure, THF was distilled off to obtain a non-aqueous resin dispersion [fine particle dispersion (W)]. The volume average particle diameter measured by “LA-920” of the fine particle dispersion (W) was 0.040 μm [SP value of molecular chain (k), that is, silicone chain: 8.5 (cal / cm ³ ) ^{1 / 2} ]. The solubility of the resin in the liquid paraffin [the concentration of the resin contained in the supernatant obtained by centrifuging the fine particle dispersion (W)] was 0.5% by weight.

<Production Example 3> [Production of resin (b1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen blowing tube, 701 parts of 1,2-propylene glycol (18.8 mol parts), 716 parts of dimethyl terephthalate (7.5 mols) Part), 180 parts (2.5 mole parts) of adipic acid and 3 parts of tetrabutoxy titanate as a condensation catalyst were added and reacted for 8 hours while distilling off methanol produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction is performed for 4 hours while distilling off the propylene glycol and water produced under a nitrogen stream, and further, the reaction is continued under a reduced pressure of 5 to 20 mmHg until the softening point reaches 150 ° C. To obtain a resin (b1) which is a polyester resin. The Mn of the resin (b1) was 8,000. The recovered propylene glycol was 316 parts (8.5 mol parts).

<Production Example 4> [Production of resin (b2)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen blowing tube, 557 parts (17.5 mole parts) of propylene glycol, 569 parts (7.0 mole parts) of dimethyl terephthalate, adipine 184 parts (3.0 parts by mole) of acid and 3 parts of tetrabutoxytitanate as a condensation catalyst were added and reacted at 180 ° C. under a nitrogen stream for 8 hours while distilling off the produced methanol. Next, while gradually raising the temperature to 230 ° C., the reaction was carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further carried out for 1 hour under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 175 parts (5.5 mole parts). Next, it is cooled to 180 ° C., 121 parts (1.5 mole parts) of trimellitic anhydride is added, and after reacting for 2 hours under normal pressure sealing, the reaction is carried out at 220 ° C. and normal pressure until the softening point is 180 ° C., A resin (b2) which was a polyester resin was obtained. The Mn of the resin (b2) was 8,500.

<Production Example 5> (Production of colorant dispersion)
Into a beaker, 20 parts of copper phthalocyanine, 4 parts of a colorant dispersant “Solspers 28000” (manufactured by Avicia Co., Ltd.), 20 parts of resin (b2) and 56 parts of acetone were stirred and dispersed uniformly. Then, copper phthalocyanine was finely dispersed to obtain a colorant dispersion. The volume average particle diameter measured with “LA-920” of the colorant dispersion was 0.2 μm.

<Production Example 6> (Production of modified wax)
In a pressure-resistant reaction vessel equipped with a stirrer, heating / cooling device, thermometer, and dropping cylinder, 454 parts of xylene, low molecular weight polyethylene “Sun Wax LEL-400” [softening point: 128 ° C., manufactured by Sanyo Chemical Industries, Ltd.] 150 The mixture was purged with nitrogen and heated to 170 ° C. with stirring. At the same temperature, 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 prepared. The solution was added dropwise over 3 hours, and further maintained at the same temperature for 30 minutes. Subsequently, xylene was distilled off under reduced pressure of 300 mmHg to obtain a modified wax. The modified wax had a graft chain SP value of 10.35 (cal / cm ³ ) ^1/2 , Mn of 1,900, Mw of 5,200, and Tg of 56.9 ° C.

<Production Example 7> (Production of wax dispersion)
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, 10 parts of paraffin wax (melting point: 73 ° C.), 1 part of denatured wax and 33 parts of acetone were added, and the temperature was raised to 78 ° C. with stirring. After stirring at the same temperature for 30 minutes, the mixture was cooled to 30 ° C. over 1 hour to crystallize the paraffin wax into fine particles, and wet pulverized with Ultra Viscomil (manufactured by Imex) to obtain a wax dispersion.

<Production Example 8> [Production of resin solution (1)]
In a reaction vessel equipped with a stirrer, 10 parts of resin (b1) and 10 parts of acetone were added and stirred to uniformly disperse to obtain a resin solution (1).

<Production Example 9> [Production of resin solution (2)]
Into a reaction vessel equipped with a stirrer, 10 parts of resin (b2) and 10 parts of acetone were added and stirred to uniformly disperse to obtain a resin solution (2).

<Example 1>
A beaker is charged with 48 parts of the resin solution (1), 12 parts of the resin solution (2), 27 parts of the wax dispersion and 10 parts of the colorant dispersion, and stirred at 25 ° C. using a TK homomixer at 8,000 rpm. Resin solution (1A) was obtained.
In another beaker, 50 parts of liquid paraffin, 10 parts of the block copolymer (Z) solution and 25 parts of the fine particle dispersion (W) were added and dispersed uniformly. Next, while stirring at 10,000 rpm using a TK homomixer at 25 ° C., 75 parts of the resin solution (1A) was added and stirred for 2 minutes. The mixture was then transferred to a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, heated to 35 ° C. and distilled under a reduced pressure of 300 mmHg until the acetone concentration reached 0.5% by weight or less. To obtain an electrophotographic liquid developer (F) in which resin particles (C) in which resin particles derived from the fine particle dispersion (W) attached to the surface are coated are dispersed. The concentration of acetone was quantified by gas chromatography “GC2010” [FID method, manufactured by Shimadzu Corporation] (the same applies hereinafter).

<Comparative Example 1>
A beaker is charged with 48 parts of the resin solution (1), 12 parts of the resin solution (2), 27 parts of the wax dispersion and 10 parts of the colorant dispersion, and stirred at 8,000 rpm at 25 ° C. using a TK homomixer. Resin solution (1B) was obtained.
In another beaker, 75 parts of liquid paraffin was added, and while stirring at 10,000 rpm using a TK homomixer at 25 ° C., 75 parts of the resin solution (1B) was added and stirred for 2 minutes. The mixture was then transferred to a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, heated to 35 ° C. and distilled under a reduced pressure of 300 mmHg until the acetone concentration reached 0.5% by weight or less. The electrophotographic liquid developer (F ′) in which the resin particles (C ′) having no shell were dispersed was obtained.

<Example of physical property measurement>
The particle size distribution of the electrophotographic liquid developers (F) and (F ′) obtained in Example 1 and Comparative Example 1 was measured by “LA-920”. Further, the physical properties of the resin particles (C) and (C ′) were measured. The results are shown in Table 1.

Resin particles (C) and (C ') contained in the liquid developer for electrophotography, surface coverage, volume average particle size, coefficient of variation of volume distribution, average circularity, and solubility of resin (a) in (L) Is measured by the method described above.
The particle surface smoothness of the resin particles (C) and (C ′), the fixability and the heat resistant storage stability of the electrophotographic liquid developer (F) and (F ′) were evaluated by the following methods.

[Particle surface smoothness]
Using a scanning electron microscope (SEM), the surface of the resin particles (C) and (C ′) separated from the electrophotographic liquid developer by centrifugation was observed with photographs magnified 10,000 and 30,000 times. Evaluated by criteria.
(Double-circle): There is no unevenness | corrugation on the surface, and it is very smooth.
○: Some irregular parts are seen on the surface, but there is almost no unevenness and the surface is smooth.
(Triangle | delta): Although the whole surface has unevenness | corrugation, the particulate object derived from resin (a) cannot be confirmed.
X: The particle | grains which the surface is badly uneven as a whole, or contain resin (a) can be confirmed.

[Fixability 1]
The electrophotographic liquid developers (F) and (F ′) are hung on the paper surface and uniformly applied so as to form a bar coater (# 10, gap 22.9 μm). May be used). When this paper was passed through a pressure 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 , the temperature of occurrence of cold offset was measured.

[Fixability 2]
A release tape “Scotch Mending Tape” [manufactured by Sumitomo 3M Co., Ltd.] was adhered to the image fixed in [Fixability 1], and then the tape was peeled off, and the temperature at which image loss occurred was measured.

[Heat resistant storage stability]
After leaving the electrophotographic liquid developers (F) and (F ′) for 24 hours in a dryer temperature-controlled at 50 ° C., the particle size distribution is measured, and the change in the particle size distribution before and after heating is based on the following criteria. evaluated.
○: The particle size distribution does not change and blocking does not occur.
Δ: The particle size distribution changes, but returns to the original particle size distribution by ultrasonic dispersion (20 kHz, 200 W, 1 minute).
X: The particle size distribution has changed, and the original particle size distribution is not restored even when ultrasonic dispersion is performed.

The electrophotographic liquid developer of the present invention is also suitable as a paint, an oil-based ink for an ink jet printer, an ink for electronic paper, a cosmetic, a spacer for manufacturing an electronic component, an electrorheological fluid, and the like.

Claims (12)

It is composed of one or more film-like shell layers (P) containing the first resin (a) and one core layer (Q) containing the second resin (b), and (P) The core-shell type resin particles (C) having a weight ratio of (Q) of (1:99) to (70:30) include the structural unit (1) represented by the following general formula (I), The structural unit (2) represented by the general formula (II), the amino group of the structural unit (1), and the organic phosphoric acid compound represented by the following general formula (III) form a salt. A liquid developer for electrophotography dispersed in a non-aqueous organic solvent (L) having a relative dielectric constant of 1 to 4 at 20 ° C. in the presence of the formed block copolymer (Z).

[In the formulas (I) to (III), R ¹ is a hydrogen atom or a methyl group; R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; alkylene ^{group, - [CH (R 6)} -CH (R 7) -O] x-CH (R 6) -CH (R 7) - or _{- [(CH 2) y-} O] z- (CH 2) a group represented by y-; R ⁴ represents an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] x—R ⁸ or — [(CH ₂ ) y —O] z—R ⁸ , R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, R ⁸ is a hydrogen atom, 18 alkyl group, a benzyl group, a phenyl group, a biphenyl group, -CHO, a group represented by _-CH 2 CHO or _-CH 2 COOR ^12, R ² is an alkyl group of 1 to 5 hydrogen atoms or C; ^{R 5} and R ^{5 'are} each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, - [ A group represented by CH (R ⁹ ) —CH (R ¹⁰ ) —O] a—R ¹¹ or — [(CH ₂ ) b—O] c—R ¹¹ , wherein R ⁹ and R ¹⁰ are each independently R ¹¹ is represented by a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ^13. R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; x, z, a and c are each independently an integer of 1 to 18; y and b are each independently an integer of 1 to 5 M and n each independently represents an integer of 1 to 200; ]   The liquid developer for electrophotography according to claim 1, wherein the solubility of (a) in (L) is 1% by weight or less.   3. The liquid developer for electrophotography according to claim 1, wherein (a) is a resin having a molecular chain (k) having a solubility parameter difference of 2 or less from (L) in the side chain.   The electrophotographic liquid developer according to claim 3, wherein (a) is a resin having a (co) polymer skeleton of a vinyl monomer (m) having a molecular chain (k) and, if necessary, another vinyl monomer.   (M) has a vinyl monomer (m1) having a linear hydrocarbon chain having 12 to 27 carbon atoms, a vinyl monomer (m2) having a branched hydrocarbon chain having 12 to 27 carbon atoms, and a polydimethylsiloxane chain. 5. The electrophotographic liquid developer according to claim 4, which is at least one selected from a vinyl monomer (m3) and a vinyl monomer (m4) having a C 4-20 fluoroalkyl chain.   6. The electron according to claim 5, wherein (m) contains (m1) and (m2), and the weight ratio of (m1) to (m2) is (m1) :( m2) = 90: 10 to 10:90. Photographic liquid developer. The liquid developer for electrophotography according to claim 5 or 6, wherein (m) contains (m3) and / or (m4), and the following surface composition ratio of (C) is 0.75 to 0.98.
Surface composition ratio: Value of (C + Si + F) / (C + Si + F + O) based on element strength measured by X-ray photoelectron analysis   The electrophotographic liquid developer according to claim 1, wherein (b) is at least one selected from a vinyl resin, a polyester resin, a polyurethane resin, and an epoxy resin.   The liquid developer for electrophotography according to any one of claims 1 to 8, wherein an average value (average circularity) of the circularity R of (C) is 0.96 to 1.0.   The liquid developer for electrophotography according to any one of claims 1 to 9, wherein (Q) contains a wax (c) and / or a modified wax (d) grafted with a vinyl polymer chain.   The resin particles (C) contain the first resin (a) in the presence of the block copolymer (Z) in the non-aqueous organic solvent (L) having a relative dielectric constant of 1 to 4 at 20 ° C. Nonaqueous resin dispersion (W) in which resin particles (A) are dispersed, and a solvent solution in which the second resin (b) is dissolved in an organic solvent (M) having a solubility parameter of 8.5 to 20 The solvent solution (O2) in which the precursor (b0) of the resin (b) is dissolved in (O1) or (M) is mixed, and (O1) or (O2) is dispersed in (W). In the case of using O2), (b0) is further reacted to form resin particles (B) containing (b) in (W), whereby resin particles are formed on the surface of the resin particles (B). A non-aqueous resin dispersion (X1) of resin particles (D) having a structure with (A) attached is obtained, and (M) is further distilled off from (X1). The shell layer (P) in which (A) is coated and (A) is formed on the surface of the core layer (Q) composed of (B) is obtained. The liquid developing solution for electrophotography in any one of 10-10. Resin particles (A) containing the first resin (a) are dispersed in the non-aqueous organic solvent (L) having a relative dielectric constant of 1 to 4 at 20 ° C. in the presence of the block copolymer (Z). In the non-aqueous resin dispersion (W) and the solvent solution (O1) or (M) in which the second resin (b) is dissolved in the organic solvent (M) having a solubility parameter of 8.5 to 20 Is mixed with a solvent solution (O2) in which the precursor (b0) of the resin (b) is dissolved, (O1) or (O2) is dispersed in (W), and (O2) is used. Further, by reacting (b0) to form resin particles (B) containing (b) in (W), a resin having a structure in which the resin particles (A) are attached to the surfaces of the resin particles (B). A non-aqueous resin dispersion (X1) of particles (D) was obtained, (M) was further distilled off from (X1), (A) was formed into a film, and (B) Process for producing liquid developer for electrophotography in which resin particle (C) obtained by forming shell layer (P) having (A) coated on the surface of core layer (Q) formed is dispersed .